US7998541B2 - Benzochromene derivatives for use in liquid crystal media and as therapeutic active substances - Google Patents

Abstract

The present invention relates to benzochromene derivatives of the formula I

where the various parameters have the meaning indicated in the text, and to liquid-crystal media which comprise these compounds, and to the use of the media in electro-optical displays, in particular in TN, OCB, LCOS and/or IPS-LCDs, and to the use of the compounds and physiologically acceptable derivatives thereof as therapeutic active ingredients.

Description

The present invention relates to benzochromene derivatives, preferably mesogenic benzochromene derivatives, in particular liquid-crystalline benzochromene derivatives, and to liquid-crystalline media comprising these benzochromene derivatives. The present invention furthermore relates to liquid-crystal displays, in particular active matrix addressed liquid-crystal displays (AMDs or AM LCDs), i.e. liquid-crystal displays which are addressed by means of a matrix of active electrical elements, such as, for example, TFTs (“thin film transistors”), varistors, diodes or MIMs (“metal-insulator-metal”), and consequently have excellent image quality. For these, use is made, in particular, of the TN (“twisted nematic”) and IPS (“in plane switching”) effect, in which nematic liquid crystals of positive dielectric anisotropy (Δε) are used.

In liquid-crystal displays of this type, the liquid crystals are used as dielectrics, whose optical properties change reversibly on application of an electric voltage. Electro-optical displays which use liquid crystals as media are known to the person skilled in the art. These liquid-crystal displays use various electro-optical effects. The commonest thereof are the TN (“twisted nematic”) effect, with a homogeneous, virtually planar initial alignment of the liquid-crystal director and a nematic structure which is twisted by about 90°, the STN (“super-twisted nematic”) effect and the SBE (“supertwisted birefringence effect”) with a nematic structure which is twisted by 180° or more. In these and similar electro-optical effects, liquid-crystalline media of positive dielectric anisotropy (Δε) are used.

An electro-optical effect having excellent, low viewing-angle dependence of the contrast uses axially symmetrical micropixels (ASMs). In this effect, the liquid crystal of each pixel is surrounded in a cylindrical manner by a polymer material. This mode is particularly suitable for combination with addressing through plasma channels. Thus, in particular, large-area PA (“plasma addressed”) LCDs having good viewing-angle dependence of the contrast can be achieved.

The IPS (“in plane switching”) effect employed to an increased extent recently can use both dielectrically positive and also dielectrically negative liquid-crystal media, in a similar manner to “guest/host” displays, which can employ dyes either in dielectrically positive or dielectrically negative media, depending on the display mode used.

Furthermore, LCOS displays and displays based on a birefringence effect, such as OCB displays, are also interesting. Since the operating voltage in liquid-crystal displays in general, i.e. also in displays utilising these effects, should be as low as possible, use is made of liquid-crystal media having a large absolute value of the dielectric anisotropy which generally predominantly and in most cases even essentially consist of liquid-crystal compounds having a dielectric anisotropy having the corresponding sign, i.e. of compounds of positive dielectric anisotropy in the case of dielectrically positive media and of compounds of negative dielectric anisotropy in the case of dielectrically negative media. In the respective types of media (dielectrically positive or dielectrically negative), at most significant amounts of dielectrically neutral liquid-crystal compounds are typically employed. Liquid-crystal compounds having the opposite sign of the dielectric anisotropy to that of the dielectric anisotropy of the medium are generally employed extremely sparingly or not at all.

An exception is formed here by liquid-crystalline media for MIM (“metal-insulator-metal”) displays (Simmons, J. G., Phys. Rev. 155 No. 3, pp. 657-660 and Niwa, J. G. et al., SID 84 Digest, pp. 304-307, June 1984), in which the liquid-crystal media are addressed by means of an active matrix of thin-film transistors. In this type of addressing, which utilises the non-linear characteristic line of diode switching, a storage capacitor cannot be charged together with the electrodes of the liquid-crystal display elements (pixels), in contrast to TFT displays. In order to reduce the effect of the drop in voltage during the addressing cycle, the largest possible base value of the dielectric constant is thus necessary. In the case of dielectrically positive media, as employed, for example, in MIM-TN displays, the dielectric constant perpendicular to the molecular axis (ε_⊥) must thus be as large as possible since it determines the basic capacitance of the pixel. To this end, as described, for example, in WO 93/01253, EP 0 663 502 and DE 195 21 483, compounds of negative dielectric anisotropy are simultaneously also employed besides dielectrically positive compounds in the dielectrically positive liquid-crystal media.

A further exception is formed by STN displays, in which, for example, dielectrically positive liquid-crystal media comprising dielectrically negative liquid-crystal compounds in accordance with DE 41 00 287 are employed in order to increase the steepness of the electro-optical characteristic line.

The pixels of the liquid-crystal displays can be addressed directly, time-sequentially, i.e. in time multiplex mode, or by means of a matrix of active elements having nonlinear electrical characteristic lines.

The commonest AMDs to date use discrete active electronic switching elements, such as, for example, three-pole switching elements, such as MOS (“metal oxide silicon”) transistors or thin film transistors (TFTs) or varistors, or 2-pole switching elements, such as, for example, MIM (“metal-insulator-metal”) diodes, ring diodes or “back-to-back” diodes. Various semiconductor materials, predominantly silicon, but also cadmium selenide, are used in the TFTs. In particular, amorphous silicon or polycrystalline silicon is used.

In accordance with the present application, preference is given to liquid-crystal media of positive dielectric anisotropy (Δε>0).

1,2,3,4,4a,9,10,10a-octahydrophenanthrenes for use in liquid-crystal mixtures are known from EP 1 162 185 B1. The invention was based on the object of providing novel components for liquid-crystal mixtures in order to meet the various requirements of display manufacturers. In particular, liquid-crystal mixtures which, owing to a high dielectric anisotropy, facilitate the production of liquid-crystal displays having particularly low switching voltage are required. It can thus be seen that there is both a demand for further mesogenic compounds and also, in particular, a demand for liquid-crystal media of positive dielectric anisotropy, a large value of the dielectric anisotropy, a value of the optical anisotropy (Δn) corresponding to the particular application, a broad nematic phase, good stability to UV, heat and electric voltage, and low rotational viscosity.

This is achieved through the use of the mesogenic compounds of the formula I according to the invention

• • in which
  • G denotes —CO—O—, —CH₂—O—, —CF₂—O—, —O—CO—, —CH₂—O— or —O—CF₂—, preferably CH₂O,

• •  each, independently of one another and, if present more than once, also these independently of one another, denote
  • (a) a trans-1,4-cyclohexylene radical, in which, in addition, one or two non-adjacent CH₂ groups may be replaced by —O— and/or
  • (b) a 1,4-cyclohexenylene radical,
  • (c) a 1,4-phenylene radical, in which, in addition, one or two non-adjacent CH groups may be replaced by N, or
  • (d) naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl,
  • (e) a radical selected from the group 1,4-bicyclo[2.2.2]octylene, 1,3-bicyclo[1.1.1]pentylene, spiro[3.3]heptane-2,6-diyl and 1,3-cyclobutylene,
    • where in
    • (a) and (b), one or more —CH₂— groups, independently of one another, may each be replaced by a —CHF— or —CF₂— group, and in
    • (c) and (d), one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)=or —C(O—CF₃)═ group, preferably a —CF═ group, and preferably denote

• • L¹ to L³ each, independently of one another, denote H, halogen, CN or CF₃, preferably H, F or Cl, particularly preferably H or F, and very particularly preferably L¹ and/or L² denote F and L³ denotes H,

• •  denotes a 1,4-trans-cyclohexane-1,2,4-triyl radical, in which, in addition, one or two non-adjacent CH₂ groups may be replaced by —O— and/or —S—, and one or more —CH₂— groups, in each case independently of one another, may each be replaced by a —CHF— or —CF₂— group, and the —CH< group may be replaced by a —CF< group, and which may optionally contain one, two or three C—C double bonds, where, in this case, one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group, preferably a —CF═ group,
  • R¹ and R² each, independently of one another, denote alkyl or alkoxy having 1 to 15 C atoms, alkoxyalkyl, alkenyl or alkenyloxy having 2 to 15 C atoms, alkynyl or alkynyloxy having 2 to 15 C atoms, H, halogen, —CN, —SCN, —NCS, —OCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂, an alkyl group having 1 to 15 C atoms which is monosubstituted by —CN or —CF₃ or at least mono-substituted by halogen, where, in addition, one or more CH₂ groups, in each case independently of one another, may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

• •  —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O nor S atoms are linked directly to one another, preferably one of
  • R¹ and R² denotes alkyl or alkoxy having 1 to 12 C atoms, alkoxyalkyl, alkenyl or alkenyloxy having 2 to 12 C atoms and the other, independently of the first, denotes halogen, —CN, —SCN, —NCS, —OCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂,
  • Z¹ and Z² each, independently of one another and, if present more than once, also these independently of one another, denote —CH₂—CH₂—, —(CH₂)₄—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —CO—O—, —O—CO—, —CH₂—O—, —O—CH₂—, —CF₂—O—, —O—CF₂—, or a combination of two of these groups, where no two O atoms are bonded to one another, preferably —(CH₂)₄—, —CH₂—CH₂—, —CF₂—CF₂—, —CH═CH—, —CF═CF—, —C≡C—, —CH₂—O—, —CF₂—O— or a single bond, particularly preferably —CH₂—O—, —CH₂—CH₂—, —CF₂—CF₂—, —CF═CF—, —CF₂—O— or a single bond, and
  • n and m each denote 0, 1 or 2, where
  • n+m denotes 0, 1, 2 or 3, preferably 0, 1 or 2, particularly preferably 0 or 1.

Particular preference is given to liquid-crystal compounds of the formula I of positive dielectric anisotropy.

Preference is furthermore given to compounds of the formula I in which the structural element

denotes

in which the parameters have the meaning given above under formula I, and

• • L⁴ and L⁵ each, independently of one another, denote H or F, and preferably
    in (a) one of
  • L¹ and L² denotes F or both denote F,
    in (b) one or more, preferably two or three, of
  • L¹, L² and L⁴ denote F.

Preference is furthermore given to the compounds of the formula I which contain the structural element (a).

Very particular preference is given to liquid-crystal compounds of the formula I of the sub-formulae I-A and I-B, particularly I-A,

in which the parameters have the meaning given above under formula I, and the second aromatic ring in formula I-B may optionally be mono- or polysubstituted by F, and preferably one or both of

• • L¹ and L² denotes F.

Very particular preference is given to liquid-crystal compounds of the formula I of the sub-formulae I-A1 to I-A3 and I-B1 to I-B3, particularly of the formulae I-A1 to I-A3,

in which the parameters have the meaning given above under formula I, and the second aromatic ring in the formulae I-B1 to I-B3 may optionally be mono- or polysubstituted by F, and preferably one or both of

• • L¹ and L² denotes F.

Preference is given to compounds of the formula I, preferably selected from the group of the compounds of the formulae I-A1 to I-A3 and I-B1 to I-B3, in which

the sum n+m is 0 or 1, preferably 1.

A preferred embodiment is represented by the compounds of the formula I in which the sum n+m is 1 and preferably

m or n denotes 1,

denotes

• Z preferably denotes —(CH₂)₄—, —CH₂—CH₂—, —CF₂—CF₂—, —CH═CH—, —CF═CF—, —C≡C—, —CH₂—O—, —CF₂—O— or a single bond, particularly preferably —CH₂—O—, —CH₂—CH₂—, —CF₂—CF₂—, —CF═CF—, —CF₂—O— or a single bond,
  and L, R¹ and R² have the meaning given above for formula I, and L preferably denotes F.

Particular preference is given to compounds of the formula I, preferably selected from the group of the compounds of the formulae I-A1 to I-A3 and I-B1 to I-B3, in which

n and m both denote 0, and

L¹ to L³, R¹ and R² have the meaning given above for the corresponding formula and L¹ and/or L² preferably denote F.

Compounds of the formula I containing branched wing groups R¹ and/or R² may occasionally be of importance owing to better solubility in the usual liquid-crystalline base materials, but in particular as chiral dopants if they are optically active. Smectic compounds of this type are suitable as components of ferroelectric materials. Compounds of the formula I having SA phases are suitable, for example, for thermally addressed displays.

If R¹ and/or R² denote an alkyl radical and/or an alkoxy radical, this may be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6 or 7 C atoms and accordingly preferably denotes ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy, furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.

Oxaalkyl or alkoxyalkyl preferably denotes straight-chain 2-oxapropyl (=methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

If R¹ and/or R² denote an alkyl radical in which one CH₂ group has been replaced by —CH═CH—, this may be straight-chain or branched. It is preferably straight-chain and has 2 to 10 C atoms. Accordingly, it denotes, in particular, vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl, oct-1-, -2-, -3-, -4-, -5-, -6- or -7-enyl, non-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl, or dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.

If R¹ and/or R² denote an alkyl radical in which one CH₂ group has been replaced by —O— and one has been replaced by —CO—, these are preferably adjacent. These thus contain an acyloxy group —CO—O— or an oxycarbonyl group —O—CO—. These are preferably straight-chain and have 2 to 6 C atoms. Accordingly, they denote, in particular, acetoxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetoxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetoxypropyl, 3-propionyloxypropyl, 4-acetoxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxycarbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl or 4-(methoxycarbonyl)butyl.

If R¹ and/or R² denote an alkyl radical in which one CH₂ group has been replaced by unsubstituted or substituted —CH═CH— and an adjacent CH₂ group has been replaced by CO or CO—O or O—CO, this may be straight-chain or branched. It is preferably straight-chain and has 4 to 13 C atoms. Accordingly, it denotes, in particular, acryloyloxymethyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxynonyl, 10-acryloyloxydecyl, methacryloyloxymethyl, 2-methacryloyloxyethyl, 3-methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacryloyloxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl, 8-methacryloyloxyoctyl or 9-methacryloyloxynonyl.

If R¹ and/or R² denote an alkyl or alkenyl radical which is mono-substituted by CN or CF₃, this radical is preferably straight-chain. The substitution by CN or CF₃ is in any desired position.

If R¹ and/or R² denote an alkyl or alkenyl radical which is at least mono-substituted by halogen, this radical is preferably straight-chain, and halogen is preferably F or Cl. In the case of polysubstitution, halogen is preferably F. The resultant radicals also include perfluorinated radicals. In the case of monosubstitution, the fluorine or chlorine substituent may be in any desired position, but is preferably in the ω-position.

Branched groups generally contain not more than one chain branch. Preferred branched radicals R are isopropyl, 2-butyl (=1-methylpropyl), isobutyl (=2-methylpropyl), 2-methylbutyl, isopentyl (=3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexyloxy, 1-methylhexyloxy and 1-methylheptyloxy.

If R¹ and/or R² represent an alkyl radical in which two or more CH₂ groups have been replaced by —O— and/or —CO—O—, this may be straight-chain or branched. It is preferably branched and has 3 to 12 C atoms. Accordingly, it denotes, in particular, biscarboxymethyl, 2,2-biscarboxyethyl, 3,3-biscarboxypropyl, 4,4-biscarboxybutyl, 5,5-biscarboxypentyl, 6,6-biscarboxyhexyl, 7,7-biscarboxyheptyl, 8,8-biscarboxyoctyl, 9,9-biscarboxynonyl, 10,10-biscarboxydecyl, bis(methoxycarbonyl)methyl, 2,2-bis(methoxycarbonyl)ethyl, 3,3-bis(methoxycarbonyl)propyl, 4,4-bis(methoxycarbonyl)butyl, 5,5-bis(methoxycarbonyl)pentyl, 6,6-bis(methoxycarbonyl)hexyl, 7,7-bis(methoxycarbonyl)heptyl, 8,8-bis(methoxycarbonyl)octyl, bis(ethoxycarbonyl)methyl, 2,2-bis(ethoxycarbonyl)ethyl, 3,3-bis(ethoxycarbonyl)propyl, 4,4-bis(ethoxycarbonyl)butyl or 5,5-bis(ethoxycarbonyl)phenyl.

Particular preference is given to compounds of the formula I in which n=0 or 1 and m=0 and R¹ denotes methyl, ethyl, propyl, butyl, pentyl, vinyl, 1E-propenyl, 1E-butenyl or 1E-pentenyl, and to media comprising these compounds. Of these compounds, the alkyl-substituted compounds are particularly preferably employed.

The compounds of the formula I may be in the form of stereoisomers owing to asymmetrically substituted carbon atoms in ring B. The invention relates to all isomers, both in pure form, as a racemate and also as a mixture of diastereomers or enantiomers. Optically active compounds of the formula I can also be used as dopants in liquid-crystal mixtures.

The compounds of the formula I are synthesised (see Schemes Ia to Ic and II to IX) by the processes described in the literature (Houben Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg Thieme Verlag, Stuttgart, N.Y., 4th Edn. 1993. Regarding Scheme II, see also DE 10 2004 004 228 (A) and Taugerbeck, M. Klasen-Memmer, Application Number 10 2005 031 554.2).

In the following schemes, the compounds of the formula I are abbreviated to compounds 1. Compounds 1b and 1c here are accessible from the lactones 1a. Thus, 1b is obtained either directly by reduction of 1a using sodium borohydride in the presence of boron trifluoride or in two steps, for example by reduction of 1a to the lactol 2 and subsequent treatment with triethylsilane in the presence of boron trifluoride, or by reduction of 1a to the diol 3 and subsequent etherification, for example by treatment with acids or by Mitsunobu reaction with triphenylphosphine and diethyl azodicarboxylate (see Schemes Ia to Ic).

in which, as in the following schemes, unless explicitly indicated otherwise,

• R¹ and R² each, independently of one another, have the meanings indicated above for R¹ and R² respectively in the case of formula I and the other parameters each have the corresponding meanings indicated above in the case of formula I.

The difluoroether 1c is obtained, for example, either by reaction of the lactones 1a with Lawesson's reagent to give 4 and subsequent treatment with DAST or with NBS in the presence of Ohla's reagent (W. H. Bunnelle, B. R. McKinnis, B. A. Narayanan, J. Org. Chem. 1990, 55, pp. 768-770) (see Scheme II) or analogously to the process described in A. Taugerbeck, M. Klasen-Memmer, Application Number 10 2005 031 554.2 by fluorodesulfuration of dithioorthoesters of type 5 using an oxidant, such as, for example, bromine, NBS, DBH, inter alia, in the presence of a fluoride ion source, such as HF/pyridine complex, triethylamine trishydrogen-fluoride, etc. (see Scheme III).

The lactones 1a can be prepared as described by S. Sethna, R. Phadke, Org. React. 1953, 7, p. 1 by Pechmann condensation of phenol derivatives or resorcinols with β-ketoesters of type 6 (V. H. Wallingford, A. H. Homeyer, D. M. Jones, J. Am. Chem. Soc. 1941, 63, pp. 2252-2254) and subsequent hydrogenation (Scheme IV).

An alternative reduction of the compounds 8 using lithium in ammonia is described in D. J. Collins, A. G. Ghingran, S. B. Rutschmann, Aust. J. Chem. 1989, 42, pp. 1769-1784.

The compounds 8 are also obtainable by the method of P. Sellés, U. Mueller, Org. Lett. 2004, 6, pp. 277-279 by Suzuki coupling from enol triflates 9 (see Scheme V). The compounds 9 can be obtained from the ketoesters 6 described above by treatment with trifluoromethanesulfonic anhydride in the presence of a base, such as, for example, collidine (E. Piers, H. L. A. Tse, Tetrahedron Lett. 1984, 25, 3155-3158). The boronic acids 10 are accessible, for example, from the corresponding alkyl bromides described in A. Taugerbeck, M. Klasen-Memmer, DE102004004228 by bromine/lithium exchange and subsequent reaction with trimethyl borate.

The compounds 1a are obtained after hydrogenation as an isomer mixture, which can be separated by conventional methods, crystallisation and/or chromatography. Compounds having the 6aR*,8R*,10aS* configuration can be obtained as shown in Scheme VI in two additional synthesis steps and by the method of D. J. Collins, A. G. Ghingran, S. B. Rutschmann, Aust. J. Chem. 1989, 42, pp. 1769-1784 by base-catalysed isomerisation, where it may be advantageous firstly to open the lactone ring by saponification analogously to J. M. Fevig et al., Bioorg. Med. Chem. Lett. 1996, 6, pp. 295-300 and to close it again after base-catalysed isomerisation is complete.

More highly unsaturated or aromatic compounds 1a can be obtained analogously to the synthesis shown in Scheme IV (see Scheme VII). Corresponding access to dielectrically negative compounds is disclosed in A. Taugerbeck, M. Klasen-Memmer, Application Number DE 10 2005 031 554.2.

An alternative synthesis strategy is shown in Schemes VIII and IX, where firstly the ether or ester function is formed starting from precursors 9 or 17 substituted in a suitable manner, and the biphenyl system is built up in a second step by, for example, Suzuki coupling (Scheme VIII) or Heck reaction (Scheme IX).

Examples of structures of preferred compounds of the formula I, in which R has the meaning given for R¹ under formula I and preferably denotes alkyl having 1 to 12 C atoms, particularly preferably having 1 to 7 C atoms, or alkenyl having 2 to 7 C atoms and very particularly preferably n-alkyl, including methyl, or 1E-alkenyl, including vinyl, are given below.

Further examples of structures of preferred compounds of the formula I, in which R has the meaning given for R¹ under formula I and preferably denotes alkyl having 1 to 12 C atoms, particularly preferably having 1 to 7 C atoms, or alkenyl having 2 to 7 C atoms and very particularly n-alkyl, including methyl, or 1E-alkenyl, including vinyl, are given below.

Compounds of the formula I according to the invention may be chiral owing to their molecular structure and can accordingly occur in various enantiomeric forms. They can therefore be in racemic or optically active form.

Since the pharmaceutical efficacy of the racemates or stereoisomers of the compounds according to the invention may differ, it may be desirable to use the enantiomers. In these cases, the end product or alternatively even the intermediates can be separated into enantiomeric compounds by chemical or physical measures known to the person skilled in the art or even employed as such in the synthesis.

In the case of racemic amines, diastereomers are formed from the mixture by reaction with an optically active resolving agent. Suitable resolving agents are, for example, optically active acids, such as the R and S forms of tartaric acid, diacetyltartaric acid, dibenzoyltartaric acid, mandelic acid, malic acid, lactic acid, suitably N-protected amino acids (for example N-benzoylproline or N-benzenesulfonylproline) or the various optically active camphorsulfonic acids. Also advantageous is chromatographic enantiomer separation with the aid of an optically active resolving agent (for example dinitrobenzoylphenylglycine, cellulose triacetate or other derivatives of carbohydrates or chirally derivatised methacrylate polymers immobilised on silica gel). Suitable eluents for this purpose are aqueous or alcoholic solvent mixtures, such as, for example, hexane/isopropanol/acetonitrile, for example in the ratio 82:15:3.

The invention encompasses not only the said compounds, but also mixtures and compositions which, besides these compounds according to the invention, also comprise other pharmacological active ingredients or adjuvants which are able to influence the primary pharmacological action of the compounds according to the invention in the desired manner.

The compounds according to the invention can be employed as medicament active ingredients in human or veterinary medicine, in particular for the prophylaxis or therapy of diseases which can be influenced by the central-nervous action of the compounds.

The compounds according to the invention can particularly preferably be employed for treating sexual disorders or increasing sexual performance, diarrhoea, nicotine dependence, inflammatory CNS diseases (demyelination, viral meningitis, multiple sclerosis, Guillain-Barré syndome) and accident-induced brain injuries or head injuries, appetence disorders, i.e. dependences of various types (drugs, alcohol, sugar), bulimia and any consequences thereof (obesity, diabetes).

They are furthermore active against hypertension or act against anxiety states and/or depression, as sedative, tranquilliser, analgesic, antiemetic or they have an inflammation-inhibiting action.

The central-nervous action can be demonstrated by administration to rats in doses of 0.1-1000 mg/kg, preferably of 1-100 mg/kg. Effects such as reduced spontaneous motor activity are observed, where the requisite dose depends both on the efficacy of the compound and also on the body weight of the experimental animal.

The invention accordingly relates to compounds of the formulae defined above and below and in the claims, including physiologically acceptable salts thereof, as medicaments, diagnostic agents or reagents.

The invention also relates to corresponding pharmaceutical compositions which comprise at least one medicament of the formula I and optionally excipients and/or adjuvants. Suitable excipients are organic or inorganic substances which are suitable for enteral (for example oral), parenteral or topical administration or for administration in the form of an inhalation spray and do not react with the novel compounds, for example water, vegetable oils, benzyl alcohols, alkylene glycols, polyethylene glycols, glycerol triacetate, gelatine, carbohydrates, such as lactose or starch, magnesium stearate, talc and Vaseline. Suitable for oral use are, in particular, tablets, pills, dragees, capsules, powders, granules, syrups, juices or drops, suitable for rectal use are suppositories, suitable for parenteral use are solutions, preferably oily or aqueous solutions, furthermore suspensions, emulsions or implants, and suitable for topical use are ointments, creams or powders. The novel compounds may also be lyophilised and the resultant lyophilisates used, for example, for the preparation of injection preparations. The compositions indicated may have been sterilised and/or comprise adjuvants, such as lubricants, preservatives, stabilisers and/or wetting agents, emulsifiers, salts for modifying the osmotic pressure, buffer substances, colorants, flavours and/or a plurality of further active ingredients, for example one or more vitamins.

For administration as inhalation spray, it is possible to use sprays which comprise the active ingredient either dissolved or suspended in a propellant gas or propellant-gas mixture (for example CO₂). The active ingredient here is advantageously used in micronised form, where one or more additional physiologically tolerated solvents may be present, for example ethanol. Inhalation solutions can be administered with the aid of conventional inhalers.

The substances according to the invention can generally be administered analogously to other, commercially available THC analogues, preferably in doses of between about 0.05 and 500 mg, in particular between 0.5 and 100 mg, per dosage unit. The daily dose is preferably between about 0.01 and 20 mg/kg of body weight. However, the specific dose for each patient depends on a very wide variety of factors, for example on the efficacy of the specific compound employed, on the age, body weight, general state of health, sex, on the diet, on the administration time and method, on the excretion rate, medicament combination and severity of the particular disease to which the therapy applies.

Furthermore, the novel compounds of the formula I can be used in analytical biology and molecular biology.

Specific ligand binding to the receptors is defined as the difference between complete binding and non-specific binding, which is determined in the presence of an excess of unlabelled ligands (see, for example, MUNRO, S., THOMAS, K. L. and ABU-SHAAR, M. (1993), Molecular characterization of a peripheral receptor for cannabinoids. Nature, 365: 61-65. RINALDI-CARMONA, M., CALANDRA, B., SHIRE, D., BOUABOULA, M., OUSTRIC, D., BARTH, F., CASELLAS, P., FERRARA, P. and LE FUR, G. (1996), Characterization of two cloned human CB₁ cannabinoid receptors isoform; J. Pharmacol. Exp. Ther., 278:871-878).

The present invention also relates to liquid-crystal media which comprise one or more compound(s) of the formula I.

In a preferred embodiment, the liquid-crystal media in accordance with the present invention comprise

a) one or more dielectrically positive compound(s) of the formula I

• • in which
  • G denotes —CO—O—, —CH₂—O—, —CF₂—O—, —O—CO—, —CH₂—O— or —O—CF₂—, preferably CH₂O,

• •  each, independently of one another and, if present more than once, also these independently of one another, denote
  • (a) a trans—1,4—cyclohexylene radical, in which, in addition, one or two non—adjacent CH₂ groups may be replaced by —O— and/or —S—,
  • (b) a 1,4—cyclohexenylene radical,
  • (c) a 1,4—phenylene radical, in which, in addition, one or two non—adjacent CH groups may be replaced by N, or
  • (d) naphthalene—2,6—diyl, decahydronaphthalene—2,6—diyl and 1,2,3,4—tetrahydronaphthalene—2,6—diyl,
  • (e) a radical selected from the group 1,4—bicyclo[2.2.2]octylene, 1,3—bicyclo[1.1.1]pentylene, spiro[3.3]heptane—2,6—diyl and 1,3—cyclobutylene,
    • where in
    • (a) and (b), one or more —CH₂— groups, independently of one another, may each be replaced by a —CHF— or —CF₂— group, and in
    • (c) and (d), one or more —CH= groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)= or —C(O—CF₃)= group, preferably a —CF= group, and preferably denote

• • L¹ to L³ each, independently of one another, denote H, halogen, CN or CF₃, preferably H, F or Cl, particularly preferably H or F, and very particularly preferably L¹ and/or L² denote F and L³ denotes H,

• •  denotes a 1,4-trans-cyclohexane-1,2,4-triyl radical, in which, in addition, one or two non-adjacent CH₂ groups may be replaced by —O— and/or —S—, and one or more —CH₂— groups, in each case independently of one another, may each be replaced by a —CHF— or —CF₂— group, and the —CH< group may be replaced by a —CF< group, and which may optionally contain one, two or three C—C double bonds, where in this case one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group, preferably a —CF═ group,
  • R¹ and R² each, independently of one another, denote alkyl or alkoxy having 1 to 15 C atoms, alkoxyalkyl, alkenyl or alkenyloxy having 2 to 15 C atoms, alkynyl or alkynyloxy having 2 to 15 C atoms, H, halogen, —CN, —SCN, —NCS, —OCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂, an alkyl group having 1 to 15 C atoms which is monosubstituted by —CN or —CF₃ or at least mono-substituted by halogen, where, in addition, one or more CH₂ groups, in each case independently of one another, may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

• •  —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O nor S atoms are linked directly to one another, preferably one of
  • R¹ and R² denotes alkyl or alkoxy having 1 to 12 C atoms, alkoxyalkyl, alkenyl or alkenyloxy having 2 to 12 C atoms and the other, independently of the first, denotes halogen, —CN, —SCN, —NCS, —OCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂,
  • Z¹ and Z² each, independently of one another and, if present more than once, also these independently of one another, denote —CH₂—CH₂—, —(CH₂)₄—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —CO—O—, —O—CO—, —CH₂—O—, —O—CH₂—, —CF₂—O—, —O—CF₂—, or a combination of two of these groups, where no two O atoms are bonded to one another, preferably —(CH₂)₄—, —CH₂—CH₂—, —CF₂—CF₂—, —CH═CH—, —CF═CF—, —C≡C—, —CH₂—O—, —CF₂—O— or a single bond, particularly preferably —CH₂—O—, —CH₂—CH₂—, —CF₂—CF₂—, —CF═CF—, —CF₂—O— or a single bond, and
  • n and m each denote 0, 1 or 2, where
  • n+m denotes 0, 1, 2 or 3, preferably 0, 1 or 2, particularly preferably 0 or 1.
    b) one or more dielectrically positive compound(s) of the formula II

• • in which
  • R²¹ has the meaning given above for R¹ in the case of formula I,
  • X²¹ denotes halogen, —CN, —SCN, —NCS, —OCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂, an alkyl group having 1 to 15 C atoms which is monosubstituted by CN or CF₃ or at least monosubstituted by halogen and in which one or more CH₂ groups, in each case independently of one another, may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

• •  —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O nor S atoms are linked directly to one another, preferably F, Cl, —OCF₃, —OCF₂ or —CF₃,
  • Z²¹ and Z²² each, independently of one another, have the meaning given above for Z¹ in the case of formula I,
  • at least one of the rings present

• •  present,
  • preferably

• • denotes

• • and the others, in each case independently of one another, denote

• • preferably

• • particularly preferably

• • particularly preferably

• •  denotes

• •  if present, denotes

• • L²¹ and L²², independently of one another, denote H or F,
  • l denotes 0, 1 or 2, preferably 0 or 1;
    and optionally
    c) one or more dielectrically neutral compounds of the formula III

• • in which
  • R³¹ and R³² each, independently of one another, have the meaning given above for R¹ in the case of formula I, and
  • Z³¹, Z³² and Z³³ each, independently of one another, denote —CH₂CH₂—, —CH═CH—, —COO— or a single bond,

• •  each, independently of one another, denote

• • o and p, independently of one another, denote 0 or 1,
  • but preferably
  • R³¹ and R³² each, independently of one another, denote alkyl or alkoxy having 1-5 C atoms or alkenyl having 2-5 C atoms,

• •  each, independently of one another, denote

• • and very particularly preferably at least two of these rings denote

• • where very particularly preferably two adjacent rings are linked directly, to be precise preferably

where in the case of the phenylene ring, one or more H atoms, independently of one another, may be replaced by F or CN, preferably by F, and one or two non-adjacent CH₂ groups of the cyclohexylene ring or of one of the cyclohexylene rings may be replaced by O atoms.

The liquid-crystal media preferably comprise one or more compounds of the formula I which contain no biphenyl unit.

The liquid-crystal media particularly preferably comprise one or more compounds of the formula I

in which two adjacent rings are linked directly, to be precise preferably

where in the case of the phenylene ring, one or more H atoms, independently of one another, may be replaced by F or CN, preferably by F, and one or two non-adjacent CH₂ groups of the cyclohexylene ring or of one of the cyclohexylene rings may be replaced by O atoms.

In a preferred embodiment, which may be identical with the embodiments just described, the liquid-crystal media comprise one or more compounds selected from the group of the compounds of the formula I-3.

The liquid-crystal medium preferably comprises one or more compounds selected from the group of the compounds of the formulae II-1 to II-4

in which
R²¹, X²¹, Z¹², Z²², L²¹, L²²,

and l each have the meaning given above in the case of formula II, and

• • L²³ and L²⁴, independently of one another, denote H or F, and
    in the case of formula II-4,

• • preferably denotes an aromatic ring.

Particularly preferably,

• • R²¹ is alkyl or alkoxy, preferably having 1-5 C atoms, preferably alkyl, and
  • in the case where I=0,
  • Z²² is —CF₂O—, —CO—O— or a single bond, particularly preferably a single bond,
  • in the case where I=1 or 2,
  • Z²¹ and Z²² are both a single bond or Z²² or one of the Z²¹ present is —CO—O—, —CF₂O— or —CH═CH—, preferably —CO—O— or —CF₂O—, particularly preferably —CF₂O—, and the others are single bond.

The liquid-crystal medium especially preferably comprises one or more compounds selected from the group of the compounds of the formulae II-1a to II-1h, II-2a to II-2d, II-3a and III-3b and II-4a to II-4c

in which
R²¹ and X²¹ each have the meaning given above in the case of formula II, and

• • L²³ to L²⁶, independently of one another, denote H or F.

The liquid-crystal medium particularly preferably comprises one or more compounds selected from the group of the compounds of the formulae III-1 to III-3:

in which R³¹, R³², Z³²,

each have the meaning indicated above for formula III.

The liquid-crystal medium especially preferably comprises one or more compounds selected from the group of the compounds of the formulae III-1a to III-1d, III-1e, III-2a to III-2g, III-3a to III-3d and III-4a:

in which n and m each, independently of one another, denote 1 to 5, and o and p each, independently both thereof and of one another, denote 0 to 3,

in which R³¹ and R³³ each have the meaning indicated above under formula III, preferably the meaning indicated under formula III-1, and the phenyl rings, in particular in the compounds III-2g and III-3c, may optionally be fluorinated, but not in such a way that the compounds are identical with those of the formula II and its sub-formulae. R³¹ is preferably n-alkyl having 1 to 5 C atoms, especially preferably having 1 to 3 C atoms, and R³² is preferably n-alkyl or n-alkoxy having 1 to 5 C atoms or alkenyl having 2 to 5 C atoms. Of these, especial preference is given to compounds of the formulae III-1a to III-1d.

Preferred fluorinated compounds of the formulae III-2g and III-3c are the compounds of the formulae III-2g′ and III-3c′

in which R³¹ and R³³ each have the meaning indicated above under formula III, preferably the meaning indicated under formula III-2g or III-3c.

In the present application, the term compounds is taken to mean both one compound and a plurality of compounds, unless expressly stated otherwise.

The liquid-crystal media according to the invention preferably have nematic phases of in each case from at least −20° C. to 80° C., preferably from −30° C. to 85° C. and very particularly preferably from −40° C. to 100° C. The term “have a nematic phase” here is taken to mean firstly that no smectic phase and no crystallisation are observed at low temperatures at the corresponding temperature and secondly also that no clearing occurs on heating from the nematic phase. The investigation at low temperatures is carried out in a flow viscometer at the corresponding temperature and checked by storage in test cells having a layer thickness corresponding to the electro-optical application for at least 100 hours. At high temperatures, the clearing point is measured in capillaries by conventional methods.

Furthermore, the liquid-crystal media according to the invention are characterised by low optical anisotropy values.

The term “alkyl” preferably encompasses straight-chain and branched alkyl groups having 1 to 7 carbon atoms, in particular the straight-chain groups methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. Groups having 2 to 5 carbon atoms are generally preferred.

The term “alkenyl” preferably encompasses straight-chain and branched alkenyl groups having 2 to 7 carbon atoms, in particular the straight-chain groups. Particularly preferred alkenyl groups are C₂- to C₇-1E-alkenyl, C₄- to C₇-3E-alkenyl, C₅- to C₇-4-alkenyl, C₆- to C₇-5-alkenyl and C₇-6-alkenyl, in particular C₂- to C₇-1E-alkenyl, C₄- to C₇-3E-alkenyl and C₅- to C₇-4-alkenyl. Examples of further preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 carbon atoms are generally preferred.

The term “fluoroalkyl” preferably encompasses straight-chain groups having a terminal fluorine, i.e. fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. However, other positions of the fluorine are not excluded.

The term “oxaalkyl” or “alkoxyalkyl” preferably encompasses straight-chain radicals of the formula C_nH_2n+1—O—(CH₂)_m, in which n and m each, independently of one another, denote 1 to 6. Preferably, n is 1 and m is 1 to 6.

Compounds containing a vinyl end group and compounds containing a methyl end group have low rotational viscosity.

In the present application, the term dielectrically positive compounds denotes compounds having a Δε of >1.5, the term dielectrically neutral compounds denotes those in which −1.5≦Δε≦1.5, and the term dielectrically negative compounds denotes those having a Δε of <−1.5. The dielectric anisotropy of the compounds is determined here by dissolving 10% of the compounds in a liquid-crystalline host and determining the capacitance of this mixture at 1 kHz in at least one test cell with a layer thickness of about 20 μm having a homeotropic surface alignment and at least one test cell with a layer thickness of about 20 μm having a homogeneous surface alignment. The measurement voltage is typically 0.5 V to 1.0 V, but is always less than the capacitive threshold of the respective liquid-crystal mixture.

The host mixture used for determining the applicationally relevant physical parameters is ZLI-4792 from Merck KGaA, Germany. As an exception, the determination of the dielectric anisotropy of dielectrically negative compounds is carried out using ZLI-2857, likewise from Merck KGaA, Germany. The values for the respective compound to be investigated are obtained from the change in the properties, for example the dielectric constants, of the host mixture after addition of the compound to be investigated and extrapolation to 100% of the compound employed.

The concentration employed for the compound to be investigated is 10%. If the solubility of the compound to be investigated is inadequate for this purpose, the concentration employed is, by way of exception, halved, i.e. reduced to 5%, 2.5%, etc., until the concentration is below the solubility limit.

The term threshold voltage usually relates to the optical threshold for 10% relative contrast (V₁₀). In relation to the liquid-crystal mixtures of negative dielectric anisotropy, however, the term threshold voltage is used in the present application for the capacitive threshold voltage (V₀), also known as the Freedericksz threshold, unless explicitly stated otherwise.

All concentrations in this application, unless explicitly stated otherwise, are indicated in percent by weight and relate to the corresponding mixture as a whole. All physical properties are and have been determined in accordance with “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, status November 1997, Merck KGaA, Germany, and apply to a temperature of 20° C., unless explicitly stated otherwise. Δn is determined at 589 nm and Δε at 1 kHz.

In the case of the liquid-crystal media of negative dielectric anisotropy, the threshold voltage was determined as the capacitive threshold V₀ in cells with a liquid-crystal layer aligned homeotropically by means of lecithin.

The liquid-crystal media according to the invention may, if necessary, also comprise further additives and optionally also chiral dopants in the conventional amounts. The amount of these additives employed is in total from 0% to 10%, based on the amount of the mixture as a whole, preferably from 0.1% to 6%. The concentrations of the individual compounds employed are in each case preferably from 0.1 to 3%. The concentration of these and similar additives is not taken into account when indicating the concentrations and the concentration ranges of the liquid-crystal compounds in the liquid-crystal media.

The compositions consist of a plurality of compounds, preferably 3 to 30, particularly preferably 6 to 20 and very particularly preferably 10 to 16 compounds, which are mixed in a conventional manner. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent, advantageously at elevated temperature. If the selected temperature is above the clearing point of the principal constituent, the completion of the dissolution process is particularly easy to observe. However, it is also possible to prepare the liquid-crystal mixtures in other conventional ways, for example using premixes or from a so-called “multibottle” system.

By means of suitable additives, the liquid-crystal phases according to the invention can be modified in such a way that they can be employed in any type of display and in particular of TN display and IPS display that has been disclosed hitherto.

The examples below serve to illustrate the invention without representing a restriction. In the examples, the melting point T(C,N), the transition from the smectic (S) phase to the nematic (N) phase T(S,N) and the clearing point T(N,I) of a liquid-crystal substance are indicated in degrees Celsius. The various smectic phases are characterised by corresponding suffixes.

The percentages above and below are, unless explicitly stated otherwise, percent by weight, and the physical properties are the values at 20° C., unless explicitly stated otherwise.

All the temperature values indicated in this application are ° C. and all temperature differences are correspondingly differential degrees, unless explicitly stated otherwise.

In the synthesis examples and schemes, the abbreviations have the following meanings:

DAST diethylaminosulfur trifluoride,

DBH dibromodimethylhydantoin,

• DEAD diethyl azodicarboxylate,
• DIBAL diisobutylaluminium hydride,
• MTB ether methyl tert-butyl ether,
• NBS N-bromosuccinimide,
• Tf trifluoromethanesulfonyl,
• THF tetrahydrofuran.

In the present application and in the examples below, the structures of the liquid-crystal compounds are indicated by means of acronyms, the trans-formation into chemical formulae taking place in accordance with Tables A and B below. All radicals C_nH_2n+1 and C_mH_2m+1 are straight-chain alkyl radicals having n and m C atoms respectively. The coding in Table B is self-evident. In Table A, only the acronym for the parent structure is indicated. In individual cases, the acronym for the parent structure is followed, separated by a dash, by a code for the substituents R¹, R², L¹, L² and L³:

Code for R1, R2, L1, L2, L3	R1	R2	L1	L2	L3
nm	CnH2n+1	CmH2m+1	H	H	H
nOm	CnH2n+1	OCmH2m+1	H	H	H
nO•m	OCnH2n+1	CmH2m+1	H	H	H
nmFF	CnH2n+1	CmH2m+1	F	H	F
nOmFF	CnH2n+1	OCmH2m+1	F	H	F
nO•mFF	OCnH2n+1	CmH2m+1	F	H	F
nO•OmFF	OCnH2n+1	OCmH2m+1	F	H	F
n	CnH2n+1	CN	H	H	H
nN•F	CnH2n+1	CN	F	H	H
nN•F•F	CnH2n+1	CN	F	F	H
nF	CnH2n+1	F	H	H	H
nF•F	CnH2n+1	F	F	H	H
nF•F•F	CnH2n+1	F	F	F	H
nCl	CnH2n+1	Cl	H	H	H
nCl.F	CnH2n+1	Cl	F	H	H
nCl•F•F	CnH2n+1	Cl	F	F	H
nmF	CnH2n+1	CmH2m+1	F	H	H
nCF3	CnH2n+1	CF3	H	H	H
nOCF3	CnH2n+1	OCF3	H	H	H
nOCF3•F	CnH2n+1	OCF3	F	H	H
nOCF3•F•F	CnH2n+1	OCF3	F	F	H
nOCF2	CnH2n+1	OCHF2	H	H	H
nOCF2•F•F	CnH2n+1	OCHF2	F	F	H
nS	CnH2n+1	NCS	H	H	H
rVsN	CrH2r+1—CH═CH—CsH2s—	CN	H	H	H
nEsN	CrH2r+1—O—CsH2s—	CN	H	H	H
nAm	CnH2n+1	COOCmH2m+1	H	H	H
nF•Cl	CnH2n+1	F	Cl	H	H

TABLE A
PYP
PYRP
BCH
CBC
CCH
CCP
CP
CPTP
CEPTP
D
ECCP
CECP
EPCH
HP
ME
PCH
PDX
PTP
BECH
EBCH
CPC
EHP
BEP
ET

TABLE B
CCZU-n-X (X = F, Cl, —OCF3 = “OT”)
CDU-n-X (X = F, Cl, —OCF3 = “OT”)
T3n
K3n
M3n
CGP-n-X (X = F, Cl, —OCF3 = “OT”)
CGU-n-X (X = F, Cl, —OCF3 = “OT”)
CGG-n-X (X = F, Cl, —OCF3 = “OT”)
Inm
CGU-n-X (X = F, Cl, —OCF3 = “OT”)
C-nm
C15
CB15
CBC-nmF
CCN-nm
G3n
CCEPC-nm
CCPC-nm
CH-nm
HD-nm
HH-nm
NCB-nm
OS-nm
CHE
CBC-nmF
ECBC-nm
ECCH-nm
CCH-n1EM
T-nFN
GP-nO-X (X = F, Cl, —OCF3 = “OT”)
CVCC-n-m
CVCP-n-m
CVCVC-n-m
CP-V-N
CC-n-V
CCG-V-F
CPP-nV2-m
CCP-V-m
CCP-V2-m
CPP-V-m
CPP-nV-m
CPP-V2-m
CC-V-V
CC-1V-V
CC-1V-V1
CC-2V-V
CC-2V-V2
CC-2V-V1
CC-V1-V
CC-V1-1V
CC-V2-1V

EXAMPLES

The following examples are intended to explain the invention without limiting it. Above and below, percentages are percent by weight. All temperatures are indicated in degrees Celsius. Δn denotes the optical anisotropy (589 nm, 20° C.), Δε the dielectric anisotropy (1 kHz, 20° C.), H.R. the voltage holding ratio (at 100° C., after 5 minutes in the oven, 1 V). V₁₀, V₅₀ and V₉₀ (the threshold voltage, mid-grey voltage and saturation voltage respectively) and V₀ (the capacitive threshold voltage) were each determined at 20° C.

SUBSTANCE EXAMPLES Example 1 (8-Propyl-3-(3,4,5-trifluorophenyl)-7,8,9,10-tetrahydrobenzo[c]-chromen-6-one) 1.1. Preparation of 6-oxo-8-propyl-7,8,9,10-tetrahydro-6H-benzo[c]-chromen-3-yl trifluoromethanesulfonate

16.6 g (78.5 mmol) of methyl 2-oxo-5-propylcyclohexanecarboxylate, 7.65 g (69.5 mmol) of resorcinol and 5.6 ml (6.1 mmol) of phosphoryl chloride are dissolved in 55 ml of toluene and refluxed for 3 h. After hydrolysis using water, the deposited precipitate is filtered off with suction, washed with toluene and dried.

The 3-hydroxy-8-propyl-7,8,9,10-tetrahydrobenzo[c]chromen-6-one obtained is dissolved in dichloromethane, 29 ml (0.21 mol) of triethylamine are added, and 25.7 ml (0.153 mol) of trifluoromethanesulfonic anhydride are added dropwise at −78° C. The cooling is removed, the batch is stirred at room temp. for 2 h and added to ice-cold 1M hydrochloric acid. The aqueous phase is separated off and extracted with dichloromethane. The combined org. phases are washed with water until neutral and dried over sodium sulfate. Removal of the solvent under reduced pressure gives 6-oxo-8-propyl-7,8,9,10-tetrahydro-6H-benzo[c]chromen-3-yl trifluoromethanesulfonate, which is reacted without further purification.

1.2. Preparation of 8-propyl-3-(3,4,5-trifluorophenyl)-7,8,9,10-tetrahydrobenzo[c]chromen-6-one

10 g (25.6 mmol) of 6-oxo-8-propyl-7,8,9,10-tetrahydro-6H-benzo[c]-chromen-3-yl trifluoromethanesulfonate, 4.50 g (25.6 mmol) of 3,4,5-trifluorobenzeneboronic acid, 10.6 g (38.4 mmol) of sodium metaborate octahydrate, 360 mg (0.51 mmol) of bis(triphenylphosphine)palladium chloride and 50 μl of hydrazinium hydroxide are dissolved in 15 ml of water and 250 ml of THF, and the mixture is refluxed overnight. Water is added to the batch, which is extracted three times with dichloromethane. The combined org. phases are dried over sodium sulfate, the solvent is removed under reduced pressure, and the residue is filtered through silica gel and recrystallised, giving 8-propyl-3-(3,4,5-trifluorophenyl)-7,8,9,10-tetrahydrobenzo[c]chromen-6-one.

Example 2 (8-Propyl-3-(3,4,5-trifluorophenyl)-6a,7,8,9,10,10a-hexahydro-6H-benzo[c]chromene) 2.1. Preparation of ethyl 5-propyl-2-(3′,4′,5′-trifluoro-3-hydroxybiphenyl-4-yl)cyclohexanecarboxylate

10 g (26.9 mmol) of 8-propyl-3-(3,4,5-trifluorophenyl)-7,8,9,10-tetrahydrobenzo[c]chromen-6-one from Example 1 (1.2.) are dissolved in THF and hydrogenated to cessation in the presence of palladium/active carbon catalyst. The mixture is subsequently filtered, the solvent is removed under reduced pressure, and the residue is dissolved in abs. ethanol and, after addition of 5.5 g (80.7 mmol) of sodium ethoxide, refluxed overnight. After addition of water, the mixture is acidified, the solution is extracted with MTB ether and dried over sodium sulfate. The solvent is removed under reduced pressure, and the crude product is purified by crystallisation, giving ethyl 5-propyl-2-(3′,4′,5′-trifluoro-3-hydroxybiphenyl-4-yl)cyclohexanecarboxylate.

2.2. Preparation of 8-propyl-3-(3,4,5-trifluorophenyl)-6a,7,8,9,10,10a-hexahydro-6H-benzo[c]chromene

903 mg (23.8 mmol) of lithium aluminium hydride are initially introduced in 20 ml of THF, and a solution of 10 g (23.8 mmol) of ethyl 5-propyl-2-(3′,4′,5′-trifluoro-3-hydroxybiphenyl-4-yl)cyclohexanecarboxylate in 50 ml of THF is added dropwise with ice-cooling. The cooling is removed, and the batch is stirred at room temp. for 3 h, refluxed for 1 h and added to ice. After acidification using 2M sulfuric acid, the mixture is extracted three times with MTB ether, the combined org. phases are washed with water and dried over sodium sulfate. The solvent is removed under reduced pressure, and the residue is purified by chromatography on silica gel. The 3′,4′,5′-trifluoro-4-(2-hydroxymethyl-4-propylcyclohexyl)biphenyl-3-ol obtained is dissolved in 100 ml of THF, 6.24 g (23.8 mmol) of triphenylphosphine are added, and a solution of 5.3 g (26.2 mmol) of diisopropyl azodicarboxylate in 50 ml of THF is added dropwise with ice-cooling. The cooling is removed, and the batch is stirred at room temp. overnight. After addition of water, the organic phase is separated off, and the aqueous phase is extracted three times with MTB ether. The combined org. phases are washed with water and saturated sodium chloride solution and dried over sodium sulfate. The solvent is removed under reduced pressure, and the residue is purified by chromatography on silica gel, giving 8-propyl-3-(3,4,5-trifluorophenyl)-6a,7,8,9,10,10a-hexahydro-6H-benzo[c]chromene as colourless crystals.

Examples 3 to 120

Compounds of the formula:

are prepared analogously to Example 1.2.

					Phase
					sequence Δε*	T*(N, I)/
No.	R1	R2	L11	R12	T/° C.	° C.

3	CH3	F	H	H
4	CH3	F	F	H
5	CH3	F	F	F
6	CH3	Cl	H	H
7	CH3	Cl	F	H
8	CH3	Cl	F	F
9	CH3	CF3	H	H
10	CH3	CF3	F	H
11	CH3	CF3	F	F
12	CH3	OCF3	H	H
13	CH3	OCF3	F	H
14	CH3	OCF3	F	F
15	CH3	CN	H	H
16	CH3	CN	F	H
17	CH3	CN	F	F
18	C2H5	F	H	H
19	C2H5	F	F	H
20	C2H5	F	F	F
21	C2H5	Cl	H	H
22	C2H5	Cl	F	H
23	C2H5	Cl	F	F
24	C2H5	CF3	H	H
25	C2H5	CF3	F	H
26	C2H5	CF3	F	F
27	C2H5	OCF3	H	H
28	C2H5	OCF3	F	H
29	C2H5	OCF3	F	F
30	C2H5	CN	H	H
31	C2H5	CN	F	H
32	C2H5	CN	F	F
33	n-C3H7	F	H	H
34	n-C3H7	F	F	H
1.2	n-C3H7	F	F	F
35	n-C3H7	Cl	H	H
36	n-C3H7	Cl	F	H
37	n-C3H7	Cl	F	F
38	n-C3H7	CF3	H	H
39	n-C3H7	CF3	F	H
40	n-C3H7	CF3	F	F
41	n-C3H7	OCF3	H	H
42	n-C3H7	OCF3	F	H
43	n-C3H7	OCF3	F	F
44	n-C3H7	CN	H	H
45	n-C3H7	CN	F	H
46	n-C3H7	CN	F	F
47	n-C4H9	F	H	H
48	n-C4H9	F	F	H
49	n-C4H9	F	F	F
50	n-C4H9	Cl	H	H
51	n-C4H9	Cl	F	H
52	n-C4H9	Cl	F	F
53	n-C4H9	CF3	H	H
54	n-C4H9	CF3	F	H
55	n-C4H9	CF3	F	F
56	n-C4H9	OCF3	H	H
57	n-C4H9	OCF3	F	H
58	n-C4H9	OCF3	F	F
59	n-C4H9	CN	H	H
60	n-C4H9	CN	F	H
61	n-C4H9	CN	F	F
62	CH3O	F	H	H
63	CH3O	F	F	H
64	CH3O	F	F	F
65	CH3O	Cl	H	H
66	CH3O	Cl	F	H
67	CH3O	Cl	F	F
68	CH3O	CF3	H	H
69	CH3O	CF3	F	H
70	CH3O	CF3	F	F
71	CH3O	OCF3	H	H
72	CH3O	OCF3	F	H
73	CH3O	OCF3	F	F
74	CH3O	CN	H	H
75	CH3O	CN	F	H
76	CH3O	CN	F	F
77	C2H5O	F	H	H
78	C2H5O	F	F	H
79	C2H5O	F	F	F
80	C2H5O	Cl	H	H
81	C2H5O	Cl	F	H
82	C2H5O	Cl	F	F
83	C2H5O	CF3	H	H
84	C2H5O	CF3	F	H
85	C2H5O	CF3	F	F
86	C2H5O	OCF3	H	H
87	C2H5O	OCF3	F	H
88	C2H5O	OCF3	F	F
89	C2H5O	CN	H	H
90	C2H5O	CN	F	H
91	C2H5O	CN	F	F
92	CH2═CH	F	H	H
93	CH2═CH	F	F	H
94	CH2═CH	F	F	F
95	CH2═CH	Cl	H	H
96	CH2═CH	Cl	F	H
97	CH2═CH	Cl	F	F
98	CH2═CH	CF3	H	H
99	CH2═CH	CF3	F	H
100	CH2═CH	CF3	F	F
101	CH2═CH	OCF3	H	H
102	CH2═CH	OCF3	F	H
103	CH2═CH	OCF3	F	F
104	CH2═CH	CN	H	H
105	CH2═CH	CN	F	H
106	CH2═CH	CN	F	F
107	CH2═CH—O	F	H	H
108	CH2═CH—O	F	F	H
109	CH2═CH—O	F	F	F
110	CH2═CH—O	Cl	H	H
111	CH2═CH—O	Cl	F	H
112	CH2═CH—O	Cl	F	F
113	CH2═CH—O	CF3	H	H
114	CH2═CH—O	CF3	F	H
115	CH2═CH—O	CF3	F	F
116	CH2═CH—O	OCF3	H	H
117	CH2═CH—O	OCF3	F	H
118	CH2═CH—O	OCF3	F	F
119	CH2═CH—O	CN	H	H
120	CH2═CH—O	CN	F	H
121	CH2═CH—O	CN	F	F
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 122 to 240

Compounds of the formula:

are prepared analogously to Example 2.2.

					Phase sequence	T*(N, I)/
No.	R1	R2	L11	R12	Δε* T/° C.	° C.

122	CH3	F	H	H
123	CH3	F	F	H
124	CH3	F	F	F
125	CH3	Cl	H	H
121	CH3	Cl	F	H
126	CH3	Cl	F	F
127	CH3	CF3	H	H
128	CH3	CF3	F	H
129	CH3	CF3	F	F
130	CH3	OCF3	H	H
131	CH3	OCF3	F	H
132	CH3	OCF3	F	F
133	CH3	CN	H	H
134	CH3	CN	F	H
135	CH3	CN	F	F
136	C2H5	F	H	H
137	C2H5	F	F	H
138	C2H5	F	F	F
139	C2H5	Cl	H	H
140	C2H5	Cl	F	H
141	C2H5	Cl	F	F
142	C2H5	CF3	H	H
143	C2H5	CF3	F	H
144	C2H5	CF3	F	F
145	C2H5	OCF3	H	H
146	C2H5	OCF3	F	H
147	C2H5	OCF3	F	F
148	C2H5	CN	H	H
149	C2H5	CN	F	H
150	C2H5	CN	F	F
151	n-C3H7	F	H	H
152	n-C3H7	F	F	H
2.2	n-C3H7	F	F	F
153	n-C3H7	Cl	H	H
154	n-C3H7	Cl	F	H
155	n-C3H7	Cl	F	F
156	n-C3H7	CF3	H	H
157	n-C3H7	CF3	F	H
158	n-C3H7	CF3	F	F
159	n-C3H7	OCF3	H	H
160	n-C3H7	OCF3	F	H
161	n-C3H7	OCF3	F	F
162	n-C3H7	CN	H	H
163	n-C3H7	CN	F	H
164	n-C3H7	CN	F	F
165	n-C4H9	F	H	H
166	n-C4H9	F	F	H
167	n-C4H9	F	F	F
168	n-C4H9	Cl	H	H
169	n-C4H9	Cl	F	H
170	n-C4H9	Cl	F	F
171	n-C4H9	CF3	H	H
172	n-C4H9	CF3	F	H
173	n-C4H9	CF3	F	F
174	n-C4H9	OCF3	H	H
175	n-C4H9	OCF3	F	H
176	n-C4H9	OCF3	F	F
177	n-C4H9	CN	H	H
178	n-C4H9	CN	F	H
179	n-C4H9	CN	F	F
180	CH3O	F	H	H
181	CH3O	F	F	H
182	CH3O	F	F	F
183	CH3O	Cl	H	H
184	CH3O	Cl	F	H
185	CH3O	Cl	F	F
186	CH3O	CF3	H	H
187	CH3O	CF3	F	H
188	CH3O	CF3	F	F
189	CH3O	OCF3	H	H
190	CH3O	OCF3	F	H
191	CH3O	OCF3	F	F
192	CH3O	CN	H	H
193	CH3O	CN	F	H
194	CH3O	CN	F	F
195	C2H5O	F	H	H
196	C2H5O	F	F	H
197	C2H5O	F	F	F
198	C2H5O	Cl	H	H
199	C2H5O	Cl	F	H
201	C2H5O	Cl	F	F
202	C2H5O	CF3	H	H
203	C2H5O	CF3	F	H
204	C2H5O	CF3	F	F
205	C2H5O	OCF3	H	H
206	C2H5O	OCF3	F	H
207	C2H5O	OCF3	F	F
208	C2H5O	CN	H	H
209	C2H5O	CN	F	H
210	C2H5O	CN	F	F
211	CH2═CH	F	H	H
212	CH2═CH	F	F	H
213	CH2═CH	F	F	F
214	CH2═CH	Cl	H	H
215	CH2═CH	Cl	F	H
216	CH2═CH	Cl	F	F
217	CH2═CH	CF3	H	H
218	CH2═CH	CF3	F	H
219	CH2═CH	CF3	F	F
220	CH2═CH	OCF3	H	H
221	CH2═CH	OCF3	F	H
222	CH2═CH	OCF3	F	F
223	CH2═CH	CN	H	H
224	CH2═CH	CN	F	H
225	CH2═CH	CN	F	F
226	CH2═CH—O	F	H	H
227	CH2═CH—O	F	F	H
228	CH2═CH—O	F	F	F
229	CH2═CH—O	Cl	H	H
230	CH2═CH—O	Cl	F	H
231	CH2═CH—O	Cl	F	F
232	CH2═CH—O	CF3	H	H
233	CH2═CH—O	CF3	F	H
234	CH2═CH—O	CF3	F	F
235	CH2═CH—O	OCF3	H	H
236	CH2═CH—O	OCF3	F	H
237	CH2═CH—O	OCF3	F	F
238	CH2═CH—O	CN	H	H
239	CH2═CH—O	CN	F	H
240	CH2═CH—O	CN	F	F
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 241 to 359

Compounds of the formula

in which

denotes

and

• • Z¹ denotes a single bond,
    are prepared analogously to Example 1.2.

					Phase
					sequence Δε*	T*(N, I)/
No.	R1	R2	L11	R12	T/° C.	° C.

241	CH3	F	H	H
242	CH3	F	F	H
243	CH3	F	F	F
244	CH3	Cl	H	H
245	CH3	Cl	F	H
246	CH3	Cl	F	F
247	CH3	CF3	H	H
248	CH3	CF3	F	H
249	CH3	CF3	F	F
250	CH3	OCF3	H	H
251	CH3	OCF3	F	H
252	CH3	OCF3	F	F
253	CH3	CN	H	H
254	CH3	CN	F	H
255	CH3	CN	F	F
256	C2H5	F	H	H
257	C2H5	F	F	H
258	C2H5	F	F	F
259	C2H5	Cl	H	H
260	C2H5	Cl	F	H
261	C2H5	Cl	F	F
262	C2H5	CF3	H	H
263	C2H5	CF3	F	H
264	C2H5	CF3	F	F
265	C2H5	OCF3	H	H
266	C2H5	OCF3	F	H
267	C2H5	OCF3	F	F
268	C2H5	CN	H	H
269	C2H5	CN	F	H
270	C2H5	CN	F	F
271	n-C3H7	F	H	H
272	n-C3H7	F	F	H
273	n-C3H7	F	F	F
274	n-C3H7	Cl	H	H
275	n-C3H7	Cl	F	H
276	n-C3H7	Cl	F	F
277	n-C3H7	CF3	H	H
278	n-C3H7	CF3	F	H
279	n-C3H7	CF3	F	F
280	n-C3H7	OCF3	H	H
281	n-C3H7	OCF3	F	H
282	n-C3H7	OCF3	F	F
283	n-C3H7	CN	H	H
284	n-C3H7	CN	F	H
285	n-C3H7	CN	F	F
286	n-C4H9	F	H	H
287	n-C4H9	F	F	H
288	n-C4H9	F	F	F
289	n-C4H9	Cl	H	H
290	n-C4H9	Cl	F	H
291	n-C4H9	Cl	F	F
292	n-C4H9	CF3	H	H
293	n-C4H9	CF3	F	H
294	n-C4H9	CF3	F	F
295	n-C4H9	OCF3	H	H
296	n-C4H9	OCF3	F	H
297	n-C4H9	OCF3	F	F
298	n-C4H9	CN	H	H
299	n-C4H9	CN	F	H
300	n-C4H9	CN	F	F
300	CH3O	F	H	H
302	CH3O	F	F	H
303	CH3O	F	F	F
304	CH3O	Cl	H	H
305	CH3O	Cl	F	H
306	CH3O	Cl	F	F
307	CH3O	CF3	H	H
308	CH3O	CF3	F	H
309	CH3O	CF3	F	F
310	CH3O	OCF3	H	H
311	CH3O	OCF3	F	H
312	CH3O	OCF3	F	F
313	CH3O	CN	H	H
314	CH3O	CN	F	H
315	CH3O	CN	F	F
316	C2H5O	F	H	H
317	C2H5O	F	F	H
318	C2H5O	F	F	F
319	C2H5O	Cl	H	H
320	C2H5O	Cl	F	H
241	C2H5O	Cl	F	F
321	C2H5O	CF3	H	H
322	C2H5O	CF3	F	H
323	C2H5O	CF3	F	F
324	C2H5O	OCF3	H	H
325	C2H5O	OCF3	F	H
326	C2H5O	OCF3	F	F
327	C2H5O	CN	H	H
328	C2H5O	CN	F	H
329	C2H5O	CN	F	F
330	CH2═CH	F	H	H
331	CH2═CH	F	F	H
332	CH2═CH	F	F	F
333	CH2═CH	Cl	H	H
334	CH2═CH	Cl	F	H
335	CH2═CH	Cl	F	F
336	CH2═CH	CF3	H	H
337	CH2═CH	CF3	F	H
338	CH2═CH	CF3	F	F
339	CH2═CH	OCF3	H	H
340	CH2═CH	OCF3	F	H
341	CH2═CH	OCF3	F	F
342	CH2═CH	CN	H	H
343	CH2═CH	CN	F	H
344	CH2═CH	CN	F	F
345	CH2═CH—O	F	H	H
346	CH2═CH—O	F	F	H
347	CH2═CH—O	F	F	F
348	CH2═CH—O	Cl	H	H
349	CH2═CH—O	Cl	F	H
350	CH2═CH—O	Cl	F	F
351	CH2═CH—O	CF3	H	H
352	CH2═CH—O	CF3	F	H
353	CH2═CH—O	CF3	F	F
354	CH2═CH—O	OCF3	H	H
355	CH2═CH—O	OCF3	F	H
356	CH2═CH—O	OCF3	F	F
357	CH2═CH—O	CN	H	H
358	CH2═CH—O	CN	F	H
359	CH2═CH—O	CN	F	F
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 360 to 479

Compounds of the formula

in which

denotes

and

• • Z¹ denotes a single bond,
    are prepared analogously to Example 2.2.

					Phase
					sequence Δε*	T*(N, I)/
No.	R1	R2	L11	R12	T/° C.	° C.

360	CH3	F	H	H
361	CH3	F	F	H
362	CH3	F	F	F
363	CH3	Cl	H	H
364	CH3	Cl	F	H
365	CH3	Cl	F	F
366	CH3	CF3	H	H
367	CH3	CF3	F	H
368	CH3	CF3	F	F
369	CH3	OCF3	H	H
370	CH3	OCF3	F	H
371	CH3	OCF3	F	F
372	CH3	CN	H	H
373	CH3	CN	F	H
374	CH3	CN	F	F
375	C2H5	F	H	H
376	C2H5	F	F	H
377	C2H5	F	F	F
378	C2H5	Cl	H	H
379	C2H5	Cl	F	H
380	C2H5	Cl	F	F
381	C2H5	CF3	H	H
382	C2H5	CF3	F	H
383	C2H5	CF3	F	F
384	C2H5	OCF3	H	H
385	C2H5	OCF3	F	H
386	C2H5	OCF3	F	F
387	C2H5	CN	H	H
388	C2H5	CN	F	H
389	C2H5	CN	F	F
390	n-C3H7	F	H	H
391	n-C3H7	F	F	H
392	n-C3H7	F	F	F
393	n-C3H7	Cl	H	H
394	n-C3H7	Cl	F	H
395	n-C3H7	Cl	F	F
396	n-C3H7	CF3	H	H
397	n-C3H7	CF3	F	H
398	n-C3H7	CF3	F	F
399	n-C3H7	OCF3	H	H
400	n-C3H7	OCF3	F	H
401	n-C3H7	OCF3	F	F
402	n-C3H7	CN	H	H
403	n-C3H7	CN	F	H
404	n-C3H7	CN	F	F
405	n-C4H9	F	H	H
406	n-C4H9	F	F	H
407	n-C4H9	F	F	F
408	n-C4H9	Cl	H	H
409	n-C4H9	Cl	F	H
410	n-C4H9	Cl	F	F
411	n-C4H9	CF3	H	H
412	n-C4H9	CF3	F	H
413	n-C4H9	CF3	F	F
414	n-C4H9	OCF3	H	H
415	n-C4H9	OCF3	F	H
416	n-C4H9	OCF3	F	F
417	n-C4H9	CN	H	H
418	n-C4H9	CN	F	H
419	n-C4H9	CN	F	F
420	CH3O	F	H	H
421	CH3O	F	F	H
422	CH3O	F	F	F
423	CH3O	Cl	H	H
424	CH3O	Cl	F	H
425	CH3O	Cl	F	F
426	CH3O	CF3	H	H
427	CH3O	CF3	F	H
428	CH3O	CF3	F	F
429	CH3O	OCF3	H	H
430	CH3O	OCF3	F	H
431	CH3O	OCF3	F	F
432	CH3O	CN	H	H
453	CH3O	CN	F	H
434	CH3O	CN	F	F
435	C2H5O	F	H	H
436	C2H5O	F	F	H
437	C2H5O	F	F	F
438	C2H5O	Cl	H	H
439	C2H5O	Cl	F	H
440	C2H5O	Cl	F	F
441	C2H5O	CF3	H	H
442	C2H5O	CF3	F	H
443	C2H5O	CF3	F	F
444	C2H5O	OCF3	H	H
445	C2H5O	OCF3	F	H
446	C2H5O	OCF3	F	F
447	C2H5O	CN	H	H
448	C2H5O	CN	F	H
449	C2H5O	CN	F	F
450	CH2═CH	F	H	H
451	CH2═CH	F	F	H
452	CH2═CH	F	F	F
453	CH2═CH	Cl	H	H
454	CH2═CH	Cl	F	H
455	CH2═CH	Cl	F	F
456	CH2═CH	CF3	H	H
457	CH2═CH	CF3	F	H
458	CH2═CH	CF3	F	F
459	CH2═CH	OCF3	H	H
460	CH2═CH	OCF3	F	H
461	CH2═CH	OCF3	F	F
462	CH2═CH	CN	H	H
463	CH2═CH	CN	F	H
464	CH2═CH	CN	F	F
465	CH2═CH—O	F	H	H
466	CH2═CH—O	F	F	H
467	CH2═CH—O	F	F	F
468	CH2═CH—O	Cl	H	H
469	CH2═CH—O	Cl	F	H
470	CH2═CH—O	Cl	F	F
471	CH2═CH—O	CF3	H	H
472	CH2═CH—O	CF3	F	H
473	CH2═CH—O	CF3	F	F
474	CH2═CH—O	OCF3	H	H
475	CH2═CH—O	OCF3	F	H
476	CH2═CH—O	OCF3	F	F
477	CH2═CH—O	CN	H	H
478	CH2═CH—O	CN	F	H
479	CH2═CH—O	CN	F	F
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 480 to 569

Compounds of the formula:

in which

denotes

and

• • Z¹ denotes a single bond,
    are prepared analogously to the preceding examples.

					Phase
					sequence Δε*	T*(N, I)/
No.	R1	R2	L11	R12	T/° C.	° C.

480	CH3	F	H	H
481	CH3	F	F	H
482	CH3	F	F	F
483	CH3	Cl	H	H
484	CH3	Cl	F	H
485	CH3	Cl	F	F
486	CH3	CF3	H	H
487	CH3	CF3	F	H
488	CH3	CF3	F	F
489	CH3	OCF3	H	H
490	CH3	OCF3	F	H
491	CH3	OCF3	F	F
492	CH3	CN	H	H
493	CH3	CN	F	H
494	CH3	CN	F	F
495	C2H5	F	H	H
496	C2H5	F	F	H
497	C2H5	F	F	F
498	C2H5	Cl	H	H
499	C2H5	Cl	F	H
500	C2H5	Cl	F	F
501	C2H5	CF3	H	H
502	C2H5	CF3	F	H
503	C2H5	CF3	F	F
504	C2H5	OCF3	H	H
505	C2H5	OCF3	F	H
586	C2H5	OCF3	F	F
507	C2H5	CN	H	H
508	C2H5	CN	F	H
509	C2H5	CN	F	F
510	n-C3H7	F	H	H
511	n-C3H7	F	F	H
512	n-C3H7	F	F	F
513	n-C3H7	Cl	H	H
514	n-C3H7	Cl	F	H
515	n-C3H7	Cl	F	F
516	n-C3H7	CF3	H	H
517	n-C3H7	CF3	F	H
518	n-C3H7	CF3	F	F
519	n-C3H7	OCF3	H	H
520	n-C3H7	OCF3	F	H
521	n-C3H7	OCF3	F	F
522	n-C3H7	CN	H	H
523	n-C3H7	CN	F	H
524	n-C3H7	CN	F	F
525	n-C4H9	F	H	H
526	n-C4H9	F	F	H
527	n-C4H9	F	F	F
528	n-C4H9	Cl	H	H
529	n-C4H9	Cl	F	H
530	n-C4H9	Cl	F	F
531	n-C4H9	CF3	H	H
532	n-C4H9	CF3	F	H
533	n-C4H9	CF3	F	F
534	n-C4H9	OCF3	H	H
535	n-C4H9	OCF3	F	H
536	n-C4H9	OCF3	F	F
537	n-C4H9	CN	H	H
538	n-C4H9	CN	F	H
539	n-C4H9	CN	F	F
540	CH2═CH	F	H	H
541	CH2═CH	F	F	H
542	CH2═CH	F	F	F
543	CH2═CH	Cl	H	H
544	CH2═CH	Cl	F	H
545	CH2═CH	Cl	F	F
546	CH2═CH	CF3	H	H
547	CH2═CH	CF3	F	H
548	CH2═CH	CF3	F	F
549	CH2═CH	OCF3	H	H
550	CH2═CH	OCF3	F	H
551	CH2═CH	OCF3	F	F
552	CH2═CH	CN	H	H
553	CH2═CH	CN	F	H
554	CH2═CH	CN	F	F
555	CH2═CH—O	F	H	H
556	CH2═CH—O	F	F	H
557	CH2═CH—O	F	F	F
558	CH2═CH—O	Cl	H	H
559	CH2═CH—O	Cl	F	H
560	CH2═CH—O	Cl	F	F
561	CH2═CH—O	CF3	H	H
562	CH2═CH—O	CF3	F	H
563	CH2═CH—O	CF3	F	F
564	CH2═CH—O	OCF3	H	H
565	CH2═CH—O	OCF3	F	H
566	CH2═CH—O	OCF3	F	F
567	CH2═CH—O	CN	H	H
568	CH2═CH—O	CN	F	H
569	CH2═CH—O	CN	F	F
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 570 to 599

Compounds of the formula:

in which

denotes

• • L¹¹ and L¹² denote H, and
  • Z¹ denotes CF₂O,
    are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

570	CH3	F
571	CH3	Cl
572	CH3	CF3
573	CH3	OCF3
574	C2H5	F
575	C2H5	Cl
576	C2H5	CF3
577	C2H5	OCF3
578	n-C3H7	F
579	n-C3H7	Cl
580	n-C3H7	CF3
581	n-C3H7	OCF3
582	n-C4H9	F
583	n-C4H9	Cl
584	n-C4H9	CF3
585	n-C4H9	OCF3
586	n-C5H11	F
587	n-C5H11	Cl
588	n-C5H11	CF3
589	n-C5H11	OCF3
590	n-C7H15	F
591	n-C7H15	Cl
592	n-C7H15	CF3
593	n-C7H15	OCF3
594	CH2═CH	F
595	CH2═CH	Cl
596	CH2═CH	CF3
597	CH2═CH	OCF3
598	E-CH3—CH═CH	F
599	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 600 to 629

Compounds of the formula:

in which

denotes

• • L¹¹ denotes H,
  • L¹² denotes F, and
  • Z¹ denotes CF₂O,
    are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

600	CH3	F
601	CH3	Cl
602	CH3	CF3
603	CH3	OCF3
604	C2H5	F
605	C2H5	Cl
606	C2H5	CF3
607	C2H5	OCF3
608	n-C3H7	F
609	n-C3H7	Cl
610	n-C3H7	CF3
611	n-C3H7	OCF3
612	n-C4H9	F
613	n-C4H9	Cl
614	n-C4H9	CF3
615	n-C4H9	OCF3
616	n-C5H11	F
617	n-C5H11	Cl
618	n-C5H11	CF3
619	n-C5H11	OCF3
620	n-C7H15	F
621	n-C7H15	Cl
622	n-C7H15	CF3
623	n-C7H15	OCF3
624	CH2═CH	F
625	CH2═CH	Cl
626	CH2═CH	CF3
627	CH2═CH	OCF3
628	E-CH3—CH═CH	F
629	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 630 to 659

Compounds of the formula:

in which

denotes

• • L¹¹ and L¹² denote F, and
  • Z¹ denotes CF₂O,
    are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

630	CH3	F
631	CH3	Cl
632	CH3	CF3
633	CH3	OCF3
634	C2H5	F
635	C2H5	Cl
636	C2H5	CF3
637	C2H5	OCF3
638	n-C3H7	F
639	n-C3H7	Cl
640	n-C3H7	CF3
641	n-C3H7	OCF3
642	n-C4H9	F
643	n-C4H9	Cl
644	n-C4H9	CF3
645	n-C4H9	OCF3
646	n-C5H11	F
677	n-C5H11	Cl
648	n-C5H11	CF3
649	n-C5H11	OCF3
650	n-C7H15	F
651	n-C7H15	Cl
652	n-C7H15	CF3
653	n-C7H15	OCF3
654	CH2═CH	F
655	CH2═CH	Cl
656	CH2═CH	CF3
657	CH2═CH	OCF3
658	E-CH3—CH═CH	F
659	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 660 to 689

Compounds of the formula:

in which

denotes

and

• Z² denotes a single bond,
  are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

660	CH3	F
661	CH3	Cl
662	CH3	CF3
663	CH3	OCF3
664	C2H5	F
665	C2H5	Cl
666	C2H5	CF3
667	C2H5	OCF3
668	n-C3H7	F
669	n-C3H7	Cl
670	n-C3H7	CF3
671	n-C3H7	OCF3
672	n-C4H9	F
673	n-C4H9	Cl
674	n-C4H9	CF3
675	n-C4H9	OCF3
676	n-C5H11	F
677	n-C5H11	Cl
678	n-C5H11	CF3
679	n-C5H11	OCF3
680	n-C7H15	F
681	n-C7H15	Cl
682	n-C7H15	CF3
683	n-C7H15	OCF3
684	CH2═CH	F
685	CH2═CH	Cl
686	CH2═CH	CF3
687	CH2═CH	OCF3
688	E-CH3—CH═CH	F
689	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 690 to 719

Compounds of the formula:

in which

denotes

and

• Z² denotes a single bond,
  are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

690	CH3	F
691	CH3	Cl
692	CH3	CF3
693	CH3	OCF3
694	C2H5	F
695	C2H5	Cl
696	C2H5	CF3
697	C2H5	OCF3
698	n-C3H7	F
699	n-C3H7	Cl
700	n-C3H7	CF3
701	n-C3H7	OCF3
702	n-C4H9	F
703	n-C4H9	Cl
704	n-C4H9	CF3
705	n-C4H9	OCF3
706	n-C5H11	F
707	n-C5H11	Cl
708	n-C5H11	CF3
709	n-C5H11	OCF3
710	n-C7H15	F
711	n-C7H15	Cl
712	n-C7H15	CF3
713	n-C7H15	OCF3
714	CH2═CH	F
715	CH2═CH	Cl
716	CH2═CH	CF3
717	CH2═CH	OCF3
718	E-CH3—CH═CH	F
719	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 720 to 749

Compounds of the formula:

in which

denotes

and

• Z² denotes a single bond,
  are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

720	CH3	F
721	CH3	Cl
722	CH3	CF3
723	CH3	OCF3
724	C2H5	F
725	C2H5	Cl
726	C2H5	CF3
727	C2H5	OCF3
728	n-C3H7	F
729	n-C3H7	Cl
730	n-C3H7	CF3
731	n-C3H7	OCF3
732	n-C4H9	F
733	n-C4H9	Cl
734	n-C4H9	CF3
735	n-C4H9	OCF3
736	n-C5H11	F
737	n-C5H11	Cl
738	n-C5H11	CF3
739	n-C5H11	OCF3
740	n-C7H15	F
741	n-C7H15	Cl
742	n-C7H15	CF3
743	n-C7H15	OCF3
744	CH2═CH	F
745	CH2═CH	Cl
746	CH2═CH	CF3
747	CH2═CH	OCF3
748	E-CH3—CH═CH	F
749	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 750 to 779

Compounds of the formula:

in which

denotes

and

• Z² denotes a single bond,
  are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

750	CH3	F
751	CH3	Cl
752	CH3	CF3
753	CH3	OCF3
754	C2H5	F
755	C2H5	Cl
756	C2H5	CF3
757	C2H5	OCF3
758	n-C3H7	F
759	n-C3H7	Cl
760	n-C3H7	CF3
761	n-C3H7	OCF3
762	n-C4H9	F
763	n-C4H9	Cl
764	n-C4H9	CF3
765	n-C4H9	OCF3
766	n-C5H11	F
767	n-C5H11	Cl
768	n-C5H11	CF3
769	n-C5H11	OCF3
770	n-C7H15	F
771	n-C7H15	Cl
772	n-C7H15	CF3
773	n-C7H15	OCF3
774	CH2═CH	F
775	CH2═CH	Cl
776	CH2═CH	CF3
777	CH2═CH	OCF3
778	E-CH3—CH═CH	F
779	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 780 to 809

Compounds of the formula:

in which

denotes

and

• Z² denotes a single bond,
  are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

780	CH3	F
781	CH3	Cl
782	CH3	CF3
783	CH3	OCF3
784	C2H5	F
785	C2H5	Cl
786	C2H5	CF3
787	C2H5	OCF3
788	n-C3H7	F
789	n-C3H7	Cl
790	n-C3H7	CF3
791	n-C3H7	OCF3
792	n-C4H9	F
793	n-C4H9	Cl
794	n-C4H9	CF3
795	n-C4H9	OCF3
796	n-C5H11	F
797	n-C5H11	Cl
798	n-C5H11	CF3
799	n-C5H11	OCF3
800	n-C7H15	F
801	n-C7H15	Cl
802	n-C7H15	CF3
803	n-C7H15	OCF3
804	CH2═CH	F
805	CH2═CH	Cl
806	CH2═CH	CF3
807	CH2═CH	OCF3
808	E-CH3—CH═CH	F
809	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 810 to 839

Compounds of the formula:

in which

denotes

and

• Z² denotes a single bond,
  are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

810	CH3	F
811	CH3	Cl
812	CH3	CF3
813	CH3	OCF3
814	C2H5	F
815	C2H5	Cl
816	C2H5	CF3
817	C2H5	OCF3
818	n-C3H7	F
819	n-C3H7	Cl
820	n-C3H7	CF3
821	n-C3H7	OCF3
822	n-C4H9	F
823	n-C4H9	Cl
824	n-C4H9	CF3
825	n-C4H9	OCF3
826	n-C5H11	F
827	n-C5H11	Cl
828	n-C5H11	CF3
829	n-C5H11	OCF3
830	n-C7H15	F
831	n-C7H15	Cl
832	n-C7H15	CF3
833	n-C7H15	OCF3
834	CH2═CH	F
835	CH2═CH	Cl
836	CH2═CH	CF3
837	CH2═CH	OCF3
838	E-CH3—CH═CH	F
839	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 840 to 869

Compounds of the formula:

in which

denotes

and

• Z² denotes a single bond,
  are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

840	CH3	F
841	CH3	Cl
842	CH3	CF3
843	CH3	OCF3
844	C2H5	F
845	C2H5	Cl
846	C2H5	CF3
847	C2H5	OCF3
848	n-C3H7	F
849	n-C3H7	Cl
850	n-C3H7	CF3
851	n-C3H7	OCF3
852	n-C4H9	F
853	n-C4H9	Cl
854	n-C4H9	CF3
855	n-C4H9	OCF3
856	n-C5H11	F
857	n-C5H11	Cl
858	n-C5H11	CF3
859	n-C5H11	OCF3
860	n-C7H15	F
861	n-C7H15	Cl
862	n-C7H15	CF3
863	n-C7H15	OCF3
864	CH2═CH	F
865	CH2═CH	Cl
866	CH2═CH	CF3
867	CH2═CH	OCF3
868	E-CH3—CH═CH	F
869	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 870 to 899

Compounds of the formula:

in which

denotes

and

• Z² denotes a single bond,
  are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

870	CH3	F
871	CH3	Cl
872	CH3	CF3
873	CH3	OCF3
874	C2H5	F
875	C2H5	Cl
876	C2H5	CF3
877	C2H5	OCF3
878	n-C3H7	F
879	n-C3H7	Cl
880	n-C3H7	CF3
881	n-C3H7	OCF3
882	n-C4H9	F
883	n-C4H9	Cl
884	n-C4H9	CF3
885	n-C4H9	OCF3
886	n-C5H11	F
887	n-C5H11	Cl
888	n-C5H11	CF3
889	n-C5H11	OCF3
890	n-C7H15	F
891	n-C7H15	Cl
892	n-C7H15	CF3
893	n-C7H15	OCF3
894	CH2═CH	F
895	CH2═CH	Cl
896	CH2═CH	CF3
897	CH2═CH	OCF3
898	E-CH3—CH═CH	F
899	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 900 to 929

Compounds of the formula:

in which

denotes

and

• Z² denotes a single bond,
  are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

900	CH3	F
901	CH3	Cl
902	CH3	CF3
903	CH3	OCF3
904	C2H5	F
905	C2H5	Cl
906	C2H5	CF3
907	C2H5	OCF3
908	n-C3H7	F
909	n-C3H7	Cl
910	n-C3H7	CF3
911	n-C3H7	OCF3
912	n-C4H9	F
913	n-C4H9	Cl
914	n-C4H9	CF3
915	n-C4H9	OCF3
916	n-C5H11	F
917	n-C5H11	Cl
918	n-C5H11	CF3
919	n-C5H11	OCF3
920	n-C7H15	F
921	n-C7H15	Cl
922	n-C7H15	CF3
923	n-C7H15	OCF3
924	CH2═CH	F
925	CH2═CH	Cl
926	CH2═CH	CF3
927	CH2═CH	OCF3
928	E-CH3—CH═CH	F
929	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 930 to 959

Compounds of the formula:

in which

denotes

and

• Z² denotes a single bond,
  are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

930	CH3	F
931	CH3	Cl
932	CH3	CF3
933	CH3	OCF3
934	C2H5	F
935	C2H5	Cl
936	C2H5	CF3
937	C2H5	OCF3
938	n-C3H7	F
939	n-C3H7	Cl
940	n-C3H7	CF3
941	n-C3H7	OCF3
942	n-C4H9	F
943	n-C4H9	Cl
944	n-C4H9	CF3
945	n-C4H9	OCF3
946	n-C5H11	F
947	n-C5H11	Cl
948	n-C5H11	CF3
949	n-C5H11	OCF3
950	n-C7H15	F
951	n-C7H15	Cl
952	n-C7H15	CF3
953	n-C7H15	OCF3
954	CH2═CH	F
955	CH2═CH	Cl
956	CH2═CH	CF3
957	CH2═CH	OCF3
958	E-CH3—CH═CH	F
959	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 960 to 989

Compounds of the formula:

in which

denotes

• • L¹¹ and L¹² denote H, and
  • Z¹ denotes a single bond,
    are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

960	CH3	F
961	CH3	Cl
962	CH3	CF3
963	CH3	OCF3
964	C2H5	F
965	C2H5	Cl
966	C2H5	CF3
967	C2H5	OCF3
968	n-C3H7	F
969	n-C3H7	Cl
970	n-C3H7	CF3
971	n-C3H7	OCF3
972	n-C4H9	F
973	n-C4H9	Cl
974	n-C4H9	CF3
975	n-C4H9	OCF3
976	n-C5H11	F
977	n-C5H11	Cl
978	n-C5H11	CF3
979	n-C5H11	OCF3
980	n-C7H15	F
981	n-C7H15	Cl
982	n-C7H15	CF3
983	n-C7H15	OCF3
984	CH2═CH	F
985	CH2═CH	Cl
986	CH2═CH	CF3
987	CH2═CH	OCF3
988	E-CH3—CH═CH	F
989	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 990 to 1019

Compounds of the formula:

in which

denotes

• • L¹¹ denotes H,
  • L¹² denotes F and
  • Z¹ denotes a single bond,
    are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

990	CH3	F
991	CH3	Cl
992	CH3	CF3
993	CH3	OCF3
994	C2H5	F
995	C2H5	Cl
996	C2H5	CF3
997	C2H5	OCF3
998	n-C3H7	F
999	n-C3H7	Cl
1000	n-C3H7	CF3
1001	n-C3H7	OCF3
1002	n-C4H9	F
1003	n-C4H9	Cl
1004	n-C4H9	CF3
1005	n-C4H9	OCF3
1006	n-C5H11	F
1007	n-C5H11	Cl
1008	n-C5H11	CF3
1009	n-C5H11	OCF3
1010	n-C7H15	F
1011	n-C7H15	Cl
1012	n-C7H15	CF3
1013	n-C7H15	OCF3
1014	CH2═CH	F
1015	CH2═CH	Cl
1016	CH2═CH	CF3
1017	CH2═CH	OCF3
1018	E-CH3—CH═CH	F
1019	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 1020 to 1049

Compounds of the formula:

in which

denotes

• • L¹¹ denotes F,
  • L¹² denotes H and
  • Z¹ denotes a single bond,
    are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

1020	CH3	F
1021	CH3	Cl
1022	CH3	CF3
1023	CH3	OCF3
1024	C2H5	F
1025	C2H5	Cl
1026	C2H5	CF3
1027	C2H5	OCF3
1028	n-C3H7	F
1029	n-C3H7	Cl
1030	n-C3H7	CF3
1031	n-C3H7	OCF3
1032	n-C4H9	F
1033	n-C4H9	Cl
1034	n-C4H9	CF3
1035	n-C4H9	OCF3
1036	n-C5H11	F
1037	n-C5H11	Cl
1038	n-C5H11	CF3
1039	n-C5H11	OCF3
1040	n-C7H15	F
1041	n-C7H15	Cl
1042	n-C7H15	CF3
1043	n-C7H15	OCF3
1044	CH2═CH	F
1045	CH2═CH	Cl
1046	CH2═CH	CF3
1047	CH2═CH	OCF3
1048	E-CH3—CH═CH	F
1049	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

Examples 1050 to 1079

Compounds of the formula:

in which

denotes

• • L¹¹ and L¹² denote F and
  • Z¹ denotes a single bond,
    are prepared analogously to the preceding examples.

			Phase sequence Δε*
No.	R1	R2	T/° C.

1050	CH3	F
1051	CH3	Cl
1052	CH3	CF3
1053	CH3	OCF3
1054	C2H5	F
1055	C2H5	Cl
1056	C2H5	CF3
1057	C2H5	OCF3
1058	n-C3H7	F
1059	n-C3H7	Cl
1060	n-C3H7	CF3
1061	n-C3H7	OCF3
1062	n-C4H9	F
1063	n-C4H9	Cl
1034	n-C4H9	CF3
1065	n-C4H9	OCF3
1066	n-C5H11	F
1067	n-C5H11	Cl
1068	n-C5H11	CF3
1069	n-C5H11	OCF3
1070	n-C7H15	F
1071	n-C7H15	Cl
1072	n-C7H15	CF3
1073	n-C7H15	OCF3
1074	CH2═CH	F
1075	CH2═CH	Cl
1076	CH2═CH	CF3
1077	CH2═CH	OCF3
1078	E-CH3—CH═CH	F
1079	E-CH3—CH═CH	Cl
Note:
*values extrapolated from 10% solution in ZLI-4792.

MIXTURE EXAMPLES

Liquid-crystalline mixtures are prepared and investigated for their applicational properties.

Example M 1

A liquid-crystal mixture having the composition indicated in the following table was prepared and investigated. It has the properties likewise shown in the table.

Composition

		Conc./
Compound #	Abbreviation	weight-%
1	CCP-3OCF3	7
2	CCG-V-F	6
3	CCP-3F•F•F	7
4	ECCP-3F•F	12
5	ECCP-5F•F	10
6	BCH-2F•F	9
7	BCH-3F•F•F	13
8	CC-3-V1	6
9	CC-5-V	10
10	BCH-32F	7
11	BCH-52F	5
12	Comp. Ex. 1	6
Σ		100.0

Physical properties

	T(N, I) =	92.2° C.
	Δn (20° C., 589 nm) =	0.1053
	Δε (20° C., 1 kHz) =	6.6
	γ1 (20° C.) =	148 mPa · s

The liquid-crystal medium has very good applicational properties and can be employed for various AMD technologies, such as TN and IPS displays.

Claims (15)

1. A dielectrically positive compound of formula I

in which

G denotes —CO—O—, —CH₂—O—, —CF₂—O—, —O—CO—, —O—CH₂— or —O—CF₂—,

 each, independently of one another and, if present more than once, also these independently of one another, denote

(a) a trans-1,4-cyclohexylene radical, in which, in addition, one or two non-adjacent CH₂ groups may be replaced by —O— and/or —S—,

(b) a 1,4-cyclohexenylene radical,

(c) a 1,4-phenylene radical, in which, in addition, one or two non-adjacent CH groups may be replaced by N, or

(d) naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl,

(e) a radical selected from the group 1,4-bicyclo[2.2.2]octylene, 1,3-bicyclo[1.1.1]pentylene, spiro[3.3]heptane-2,6-diyl and 1,3-cyclobutylene,

where in

(a) and (b), one or more —CH₂— groups, independently of one another, may each be replaced by a —CHF— or —CF₂— group, and in

(c) and (d), one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group,

L¹ to L³ each, independently of one another, denote H, halogen, —CN or —CF₃,

 denotes a 1,4-trans-cyclohexane-1,2,4-triyl radical, which may optionally contain one, two or three C—C double bonds,

R¹ and R² each, independently of one another, denote alkyl or alkoxy having 1 to 15 C atoms, alkoxyalkyl, alkenyl or alkenyloxy having 2 to 15 C atoms, alkynyl or alkynyloxy having 2 to 15 C atoms, H, halogen, —CN, —SCN, —NCS, —OCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂, an alkyl group having 1 to 15 C atoms which is monosubstituted by —CN or —CF₃ or at least monosubstituted by halogen, where, in addition, one or more CH₂ groups, in each case independently of one another, may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

 —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O nor S atoms are linked directly to one another, and

one of R¹ or R² is halogen, —CN, —SCN, —NCS, —OCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, or —OCHF₂,

Z¹ and Z² each, independently of one another and, if present more than once, also these independently of one another, denote —CH₂—CH₂—, —(CH₂)₄—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —CO—O—, —O—CO—, —CH₂—O—, —O—CH₂—, —CF₂—O—, —O—CF₂—, or a combination of two of these groups, where no two O atoms are bonded to one another,

n and m each denote 0, 1 or 2, where

n+m denotes 0, 1, 2 or 3.

2. A compound of the formula I according to claim 1, wherein

denotes

in which the parameters have the meaning given in claim 1 and L⁴ and L⁵ each donate H.

3. A compound according to claim 1, of the sub-formulae I-A or I-B

in which the parameters have the meaning given in claim 1.

4. A compound according to claim 1, of the sub-formulae I-A1 to I-A3 or I-B1 to I-B3

in which the parameters have the meaning given in claim 1.

5. A compound according to claim 1, wherein Z¹ and Z² both denote a single bond.

6. A liquid-crystal medium, comprising one or more compounds of formula I as defined in claim 1.

7. The liquid-crystal medium according to claim 6, having a nematic phase.

8. A liquid-crystal medium, comprising a dielectrically positive compound formula I

in which

G denotes —CO—O—, —CH₂—O—, —CF₂—O—, —O—CO—, —O—CH₂— or —O—CF₂ —,

 each, independently of one another and, if present more than once, also these independently of one another, denote

(a) a trans-1,4-cyclohexylene radical, in which, in addition, one or two non-adjacent CH₂ groups may be replaced by —O— and/or —S—,

(b) a 1,4-cyclohexenylene radical,

(c) a 1,4-phenylene radical, in which, in addition, one or two non-adjacent CH groups may be replaced by N, or

(d) naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl,

(e) a radical selected from the group 1,4-bicyclor[2.2.2]octylene, 1,3-bicyclor[1.1.1]pentylene, spiror[3.3]heptane-2,6-diyl and 1,3-cyclobutylene,

where in

(a) and (b), one or more —CH₂— groups, independently of one another, may each be replaced by a —CHF—or —CF₂—group, and in

(c) and (d), one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group

L¹ to L³ each, independently of one another, denote H, halogen, —CN or —CF₃,

 denotes a 1,4-trans-cyclohexane-1,2,4-triyl radical, which may optionally contain one, two or three C—C double bonds,

R¹ and R² each, independently of one another, denote alkyl or alkoxy having 1 to 15 C atoms, alkoxyalkyl, alkenyl or alkenyloxy having 2 to 15 C atoms, alkynyl or alkynyloxy having 2 to 15 C atoms, H, halogen, —CN, —SCN, —NCS, —OCN, —SF₅, —CF₃ —CHF₂, —CH₂F, —OCF₃, —OCHF₂, an alkyl group having 1 to 15 C atoms which is monosubstituted by —CN or —CF₃ or at least monosubstituted by halogen, where, in addition, one or more CH₂ groups, in each case independently of one another, may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

 —CO—, —CO—O—, —O—CO— or —O—CO—O—in such a way that neither O nor S atoms are linked directly to one another,

Z¹ and Z² each, independently of one another and, if present more than once, also these independently of one another, denote —CH₂—CH₂—, —(CH₂)₄—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —CO—O—, —O—CO—, —CH₂—O—, —O—CH₂—, —CF₂—O—, —O—CF₂—, or a combination of two of these groups, where no two O atoms are bonded to one another,

n and m each denote 0, 1 or 2, where

n+m denotes 0, 1, 2 or 3

further comprising

one or more dielectrically positive compound(s) of formula II

in which

R²¹ has the same meaning as R¹,

X²¹ denotes halogen, —CN, —SCN, —NCS, —OCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂, an alkyl group having 1 to 15 C atoms which is monosubstituted by CN or CF₃ or at least monosubstituted by halogen and in which one or more CH₂ groups, in each case independently of one another, may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

 —CO—, —CO—O—, —O—CO— or —O—CO—O—in such a way that neither O nor S atoms are linked directly to one another,

Z²¹ and Z²² each, independently of one another, have the same meaning as Z¹,

at least one of the rings present

 denotes

and the others, in each case independently of one another, denote

L²¹ and L²², independently of one another, denote H or F,

l denotes 0, 1 or 2.

9. A liquid-crystal medium, comprising a dielectrically positive compound of Formula I

in which

G denotes —CO—O—, —CH₂—O—, —CF₂—O—, —O—CO—, —O—CH₂— or —O—CF₂,

 each, independently of one another and, if present more than once, also these independently of one another, denote

(a) a trans-1,4-cyclohexylene radical, in which, in addition, one or two non-adjacent CH₂ groups may be replaced by —O— and/or —S—,

(b) a 1,4-cyclohexenylene radical,

(c) a 1,4-phenylene radical, in which, in addition, one or two non-adjacent CH groups may be replaced by N, or

(d) naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl,

(e) a radical selected from the group 1,4-bicyclo[2.2.2]octylene, 1,3-bicyclo[1.1.1]pentylene, spiro[3.3]heptane-2,6-diyl and 1,3-cyclobutylene,

where in

(a) and (b), one or more —CH₂— groups, independently of one another, may each be replaced by a —CHF—or —CF₂—group, and in

(c) and (d), one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group,

L¹ to L³ each, independently of one another, denote H, halogen, —CN or —CF₃,

 denotes a 1,4-trans-cyclohexane-1,2,4-triyl radical, which may optionally contain one, two or three C—C double bonds,

R¹ and R² each, independently of one another, denote alkyl or alkoxy having 1 to 15 C atoms, alkoxyalkyl, alkenyl or alkenyloxy having 2 to 15 C atoms, alkynyl or alkynyloxy having 2 to 15 C atoms, H, halogen, —CN, —SCN, —NCS, —OCN, —SF₅, —CF₃ —CHF₂, —CH₂F, —OCF₃, —OCHF₂, an alkyl group having 1 to 15 C atoms which is monosubstituted by —CN or —CF₃ or at least monosubstituted by halogen, where, in addition, one or more CH₂ groups, in each case independently of one another, may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

 —CO—, —CO—O—, —O—CO— or —O—CO—O—in such a way that neither O nor S atoms are linked directly to one another,

Z¹ and Z² each, independently of one another and, if present more than once, also these independently of one another, denote —CH₂—CH₂—, —(CH₂)₄—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —CO—O——O—CO—, —CH₂—O—, —O—CH₂—, —CF₂—O—, —O—CF₂—, or a combination of two of these groups, where no two O atoms are bonded to one another,

n and m each denote 0, 1 or 2, where

n+m denotes 0, 1, 2 or 3

further comprising one or more dielectrically neutral compound(s) of formula III

in which

R³¹ and R³² each, independently of one another, have the meaning given above for R¹ in the case of formula I, and

Z³¹, Z³² and Z³³ each, independently of one another, denote —CH₂CH₂—, —CH═CH—, —COO— or a single bond,

 each, independently of one another, denote

o and p, independently of one another, denote 0 or 1,

where in the case of the phenylene ring, one or more H atoms, independently of one another, may be replaced by F or CN, and one or two non-adjacent CH₂ groups of the cyclohexylene ring or of one of the cyclohexylene rings may be replaced by O atoms.

10. An electro-optical display containing a liquid-crystal medium according to claim 6.

11. A pharmaceutical composition, comprising at least one compound of formula I according to claim 1 and/or physiologically acceptable salts or solvates thereof, and a pharmaceutically acceptable carrier.

12. A method for the treatment of diseases or symptoms which can be influenced by inhibition of cannabinoid recaptors, comprising administering to a host in need thereof an effective amount of a compound according to claim 1.

13. A method for the treatment of psychoses, anxiety disorders, depression, aprosexia, memory disorders, cognitive disorders, loss of appetite, obesity, addiction, drug dependence, neurological disorders, neurodegenerative processes, dementia, dystonia, muscle spasms, tremor, epilepsy, multiple sclerosis, traumatic brain injuries, strokes, Parkinson's, Alzheimer's, Huntington's disease, Tourette's syndrome, cerebral ischaemia, cerebral apoplexy, craniocerebral trauma, spinal cord injuries, neuroinflammatory diseases, cerebral arteriosclerosis, viral encephalitis, diseases associated with demyelination, pain , including neuropathic pain diseases, septic shock, glaucoma, cancer, diabetes, vomiting, nausea, asthma, respiratory tract diseases, gastrointestinal diseases, gastric ulcers, diarrhoea or cardiovascular diseases, comprising administering to a host in need thereof an effective amount of a compound according to claim 1.

14. The compound according to claim 1, wherein one of R¹ or R² is —F, —Cl, —CF₃ or OCF₃.

15. The compound according to claim 1, wherein R¹ and R² each, independently of one another, denote alkyl or alkoxy having 1 to 15 C atoms, alkoxyalkyl, alkenyl or alkenyloxy having 2 to 15 C atoms, alkynyl or alkynyloxy having 2 to 15 C atoms, H, halogen, —CN, —SCN, —NCS, —OCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂, an alkyl group having 1 to 15 C atoms which is monosubstituted by —CN or —CF₃ or at least monosubstituted by halogen, where, in addition, one or more CH₂ groups, in each case independently of one another, may be replaced by —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

—CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O nor S atoms are linked directly to one another, and

one of R¹ or R² is halogen, —CN, —SCN, —NCS, —OCN, —SF₅, —CF₃, —CHF₂, —CH₂F, OCF₃, or —OCHF₂.